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Catalytic upgrading of crude tall oil into a paraffin-rich liquid

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Abstract

Catalytic upgrading via hydrotreatment is an essential method to produce paraffin-range renewable feedstocks from bio-derived oils. This research approach studies the catalytic hydrotreating of crude tall oil (CTO) over a sulfided NiMo catalyst under industrial-relevant conditions in order to produce hydrocarbon fraction, a steam cracker feed with maximum amount of paraffins and high degree of deoxygenation. Initial activity of the catalyst (6 h of time on stream) has been investigated, and we report that hydrotreating experiments at most favorable tested conditions (weight hourly space velocity, WHSV = 1 h−1 and T = 350–400 °C) produces hydrocarbon fraction with 45 wt% of paraffins (n-alkanes + i-alkanes). The highest degree of deoxygenation (91 %) was achieved at WHSV = 1 h−1 and T = 350 °C. Furthermore, the potential of hydrotreated CTO for steam cracking applications has been assessed in this study in view of the achieved product distribution and degree of deoxygenation from the hydrotreating of CTO.

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References

  1. Rapra S (2012) The future of bio plastics, market forecasts to 2017, Market Research Report- 262984. Accessed 11 Nov 2013

  2. Pyl SP, Schietekat CM, Reyniers MF, Abhari R, Marin GB, Van Geem KM (2011) Biomass to olefins: cracking of renewable naphtha. Chem Eng J 176–177:178–187

    Article  Google Scholar 

  3. Kubičková I, Kubička D (2010) Utilization of triglycerides and related feedstocks for production of clean hydrocarbon fuels and petrochemicals: a review. Waste Biomass Valorization 1(3):293–308

    Article  Google Scholar 

  4. Huber GW, O’Connor P, Corma A (2007) Processing biomass in conventional oil refineries: production of high quality diesel by hydrotreating vegetable oils in heavy vacuum oil mixtures. Appl Catal 329:120–129

    Article  Google Scholar 

  5. Abhari R, Havlik PZ (2009) Hydrodeoxygenation process. US patent publication 2009/0163744

  6. Abhari R, Tomlinson HL, Roth EG (2009) Biorenewable naphtha. US patent publication 2009/0300971 A1

  7. Sunde K, Brekke A, Solberg B (2011) Environmental impacts and costs of hydrotreated vegetable oils, transesterified lipids and woody BTL—a review. Energies 4(6):845–877

    Article  Google Scholar 

  8. UPM (01.02.2012) Investor news. http://www.upm.com/EN/INVESTORS/Investor-News/Pages/UPM-to-build-the-world%E2%80%99s-first-biorefinery-producing-wood-based-biodiesel-001-Wed-01-Feb-2012-10-10.aspx. Accessed 15 Nov 2013

  9. Biofuels journal news (08.11.2010) http://www.biofuelsjournal.com/articles/Dynamic_Fuels_Opens_Renewable_Diesel_Plant_in_Geismar__LA-101073.html. Accessed 15 Nov 2013

  10. Vermeiren W, Gyseghem VN (2012) Process for the production of bio-naphtha from complex mixtures of natural occurring fats and oils. US patent publication 2012/0142983 A1

  11. Coll R, Udas S, Jacoby WA (2001) Conversion of the rosin acid fraction of crude tall oil into fuels and chemicals. Energy Fuel 15:1166–1172

    Article  Google Scholar 

  12. Sharma RK, Bakhshi NN (1991) Catalytic conversion of crude tall oil to fuels and chemicals over HZSM-5: effect of co-feeding steam. Fuel Process Technol 27:113–130

    Article  Google Scholar 

  13. Chatterjee S, Omori S, Marda S, Shastri S (2010) Process for making biodiesel from crude tall oil. US patent publication 7695532 B2

  14. Neste oil (04.04.2013) Press release http://www.nesteoil.com/default.asp?path=1;41;540;1259;1260;20492;20993. Accessed 08 Sept 2013

  15. Knuuttila P, Kukkonen P, Hotanen Ulf (2010) Method and apparatus for preparing fuel components from crude tall oil. Patent publication WO2010097519 A2

  16. Stigsson L, Naydenov V (2009) Conversion of crude tall oil to renewable feedstock for diesel range fuel compositions. European patent publication WO 2009/131510 A1

  17. Diaz MAF, Markovits RA, Markovits SA (2005) Process for refining a raw material comprising black liquor soap, crude tall oil or tall oil pitch. EP1568 760 A1

  18. Myllyoja J, Aalto P, Savolainen P, Purola V, Alopaeus V, Grönqvist J (2012) Process for the manufacture of diesel range hydrocarbons. US 8212094 B2

  19. Anthonykutty JM, Van Geem KM, Bruycker RD, 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

    Article  Google Scholar 

  20. Anthonykutty JM, Kaila R, Pyl SP, Van Geem KM, Linnekoski J, Laitinen A Rasanen J, Penttinen T, Harlin A, Krause O (2012) Catalytic upgrading of tall oil and its fractions into value hydrocarbons via hydrodeoxygenation. Paper presented at 20th European Biomass Conference and Exhibition, Milan, Italy. 10.5071/20thEUBCE2012-3CO.11.1 Pages, 1532 – 1535

  21. Pyl SP, Dijkmans T, Antonykutty JM, Reyniers MF, Harlin A, Van Geem KM, Marin GB (2012) Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils. Bioresour Technol 126:48–55

    Article  Google Scholar 

  22. Kirshner M (2005) Chemical profile: tall oil. Chem Mark Report 34

  23. De Guzman D (2006) Markets—oils, fats, & waxes. Chem Mark Report 21

  24. Beens J, Brinkman UA (2005) Comprehensive two-dimensional gas chromatography—a powerful and versatile technique. Analyst 130(2):123–127

    Article  Google Scholar 

  25. Warnqvist J (2013) Process for obtaining a diesel like fuel. EP 2602306A1

  26. Donnis B, Egeberg RG, Blom P, Knudsen KG (2009) Hydroprocessing of bio-oils and oxygenates to hydrocarbons. Understanding the reaction routes. Top Catal 52(3):229–240

    Article  Google Scholar 

  27. Kubička D, Šimáček P, Žilková N (2009) Transformation of vegetable oils into hydrocarbons over mesoporous-alumina-supported CoMo catalysts. Top Catal 52(1–2):161–168

    Article  Google Scholar 

  28. Kikhtyanin OV, Rubanov AE, Ayupov AB, Echevsky GV (2010) Hydroconversion of sunflower oil on Pd/SAPO-31 catalyst. Fuel 89(10):3085–3092

    Article  Google Scholar 

  29. Guzman A, Torres JE, Prada LP, Nunez ML (2010) Hydroprocessing of crude palm oil at pilot plant scale. Catal Today 156(1–2):38–43

    Article  Google Scholar 

  30. Rozmysłowicz B, Mäki-Arvela P, Lestari S, Simakova OA, Eränen K, Simakova IL, Murzin DY, Salmi TO (2010) Catalytic deoxygenation of tall oil fatty acids over a palladium-mesoporous carbon catalyst: a new source of biofuels. Top Catal 53:1274–1277

    Article  Google Scholar 

  31. Calvin M (1965) The Bakerian lecture, chemical evolution. Proc R Soc Lond A 288(1415):441–446

    Article  Google Scholar 

  32. Volkman JK, Barrett MS, Dunstan AG, Jeffrey SW (1993) Geochemical significance of the occurrence of dinosterol and other 4-methyl sterols in a marine diatom. Org Geochem 20:7–15

    Article  Google Scholar 

  33. Dutta RP, Schobert HH (1993) Hydrogenation/dehydrogenation reactions of rosin. Fundam Stud Coal Liquefaction 38(3):1140–1146

    Google Scholar 

  34. Zhao C, He J, Lemonidou AA, Li X, Lercher JA (2011) Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes. J Catal 280(1):8–16

    Article  Google Scholar 

  35. Şenol OI, Ryymin EM, Viljava TR, Krause AOI (2007) Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts. J Mol Catal A Chem 277(1–2):107–112

    Google Scholar 

  36. Deutsch KL (2012) Copper catalysts in the C–O hydrogenolysis of biorenewable compounds. Dissertation, Iowa State University, Ph.D

    Google Scholar 

  37. Cunningham IM, Overton KH (1974) Steric factors in the hydrogenolysis of some steroidal allylic alcohols by mixed hydrides. J Chem Soc Perkin 1(21):2458–2462

    Article  Google Scholar 

  38. Nelan DR (1980) Process for dehydrogenation of sterols to produce Δ4-3-ketosteroids. US patent publication 4226785 A

  39. Yin Y, Liu C, Tang LQ, Liu Z (2012) Recoverable Pd/C catalyst mediated dehydrogenation of sterols and an improved synthesis of 1α-hydroxydehydroepiandrosterone. Steroids 77(13):1419–1422

    Article  Google Scholar 

  40. Yuandong L, Gao L, Wen L, Zong B (2009) Recent advances in heavy oil hydroprocessing technologies. Recent Patents Chem Eng 2(1):22–36

    Article  Google Scholar 

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Acknowledgments

Jinto Manjaly Anthonykutty acknowledges the financial support from VTT graduate school. The authors acknowledge Stora Enso for supporting this research and their vision on wood-based olefins. The authors also acknowledge Erik Sandell from Nablabs Oy for his help in GC-FID analyses of acid and neutral fractions.

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Authors and Affiliations

  1. VTT Technical Research Centre of Finland, Biologinkuja 7, Espoo, PO Box 1000, FI-02044, VTT, Finland

    Jinto M. Anthonykutty, Juha Linnekoski, Ali Harlin & Antero Laitinen

  2. Department of Biotechnology and Chemical Technology, School of Chemical Technology, Aalto University, PO Box 16100, 00076, Aalto, Finland

    Juha Lehtonen

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  1. Jinto M. Anthonykutty
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  2. Juha Linnekoski
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  3. Ali Harlin
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  4. Antero Laitinen
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  5. Juha Lehtonen
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Correspondence to Jinto M. Anthonykutty.

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Anthonykutty, J.M., Linnekoski, J., Harlin, A. et al. Catalytic upgrading of crude tall oil into a paraffin-rich liquid. Biomass Conv. Bioref. 5, 149–159 (2015). https://doi.org/10.1007/s13399-014-0132-8

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  • DOI: https://doi.org/10.1007/s13399-014-0132-8

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