Research ArticleAPPLIED SCIENCES AND ENGINEERING

Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines

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Science Advances  16 Jun 2017:
Vol. 3, no. 6, e1602624
DOI: 10.1126/sciadv.1602624
  • Fig. 1 Boiling point curves of commercial diesel and biodiesel (RME) before and after isomerizing metathesis.

    The hashed areas represent the limits specified in EN 590. *, increasing decomposition; Recovery, percentage of the sample recovered in the receiving flask during distillation.

  • Fig. 2 Boiling point histogram of the product blend after isomerizing hexenolysis of RME.

    Conditions: 10.0 mmol of 1-hexene/RME (1:1), 0.05 mol % IC-1 and Ru-1, neat, 50°C, 20 hours. The mixture was hydrogenated for analysis. This histogram was overlaid with simulated curves for 1000 molecules per catalyst (≙ 0.05 mol % catalyst) of both 1-hexene and RME, with 30,000 metathesis and 7500 double-bond migration steps. ····, olefins; —, monoesters; – –, diesters.

  • Fig. 3 Carbon-chain length histograms for olefin blends obtained by isomerizing hexenolysis with different Ru catalysts.

    Conditions: 10.0 mmol of 1-hexene/RME (1:1), 0.05 mol % IC-1 and Ru-cat., neat, 50°C, 20 hours. The samples were hydrogenated for GC analysis to simplify the chromatograms.

  • Fig. 4 Simulated boiling point distribution of olefins (····), monoesters (—), and diesters (– –) and boiling point curve of the products after isomerizing ethenolysis.

    (A) Effect of the ethylene/RME ratio near equilibrium and (B) effect of the ratio of isomerization/metathesis steps per molecule in preequilibrium reactions. Recovery, percentage of the sample recovered in the receiving flask during distillation analysis.

  • Fig. 5 Isomerizing ethenolysis of RME.

    Conditions: 400 mmol of RME, ethylene stream, Ru-11, Ru-CAAC, IC-1, neat, 60°C, 16 hours.

  • Table 1 Optimization of the isomerizing ethenolysis of RME.

    Conditions for entries 3 to 12: 2.50 mmol of RME (based on methyl oleate), ethylene, Ru-cat., Ru-CAAC, IC-1, neat, 16 hours, 60°C.


    Embedded Image
    EntryRu-cat. (mol %)Ru-CAAC (mol %)IC-1 (mol %)Ethylene (ml)Reaction temperature (°C)Average MCLEvenness of the curve
    1Isomerizing hexenolysis (see above)5015.0Excellent
    2Sequential isomerizing ethenolysis5013.7Good
    3Ru-1 (0.05)0.05300 (at 6 bar)50No conversion
    4Ru-1 (0.10)0.10206018.0Poor
    5Ru-5 (0.10)0.10206015.3Fair
    6Ru-7 (0.10)0.10206015.2Good
    7Ru-11 (0.10)0.10206015.3Fair
    8Ru-5 (0.10)0.40206015.8Fair
    9Ru-7 (0.10)0.40206015.5Excellent
    10Ru-11 (0.10)0.40206015.4Excellent
    11Ru-11 (0.10)0.100.40206015.3Excellent
    12Ru-11 (0.10)0.100.40300 (at 6 bar)6014.4Excellent
    13Ru-11 (0.10)0.100.40Constant stream6012.9Excellent

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/6/e1602624/DC1

    Supplementary Materials and Methods

    Supplementary Text

    fig. S1. Ru-based metathesis catalysts tested in the isomerizing hexenolysis, including second-generation indenylidene-ruthenium complexes Umicore M41 (Ru-2) and M31 (Ru-3) and Hoveyda-type catalysts Umicore M51 (Ru-4), M72 SIMes (Ru-5), and M74 SIMes (Ru-6).

    fig. S2. Olefin blends obtained by isomerizing hexenolysis with different Ru catalysts.

    fig. S3. State-of-the-art isomerization catalysts tested in the isomerizing hexenolysis.

    fig. S4. Mass-corrected GC with IC-1.

    fig. S5. Mass-corrected GC with IC-2.

    fig. S6. Gas chromatogram with IC-3.

    fig. S7. Gas chromatogram with IC-4.

    fig. S8. Mass-corrected GC with IC-5.

    fig. S9. Mass-corrected GC with IC-6.

    fig. S10. Mass-corrected GC with IC-7.

    fig. S11. Mass-corrected GC with IC-8.

    fig. S12. Mass-corrected gas chromatogram with 0 equiv 1-hexene.

    fig. S13. Mass-corrected gas chromatogram with 0.3 equiv 1-hexene.

    fig. S14. Mass-corrected gas chromatogram with 1 equiv 1-hexene.

    fig. S15. Mass-corrected gas chromatogram with 1.5 equiv 1-hexene.

    fig. S16. Calculated boiling point curves of RME product blends after isomerizing cross-metathesis with different amounts 1-hexene, along with pure RME and petrodiesel.

    fig. S17. Boiling point curves of commercial diesel and biodiesel (RME) before and after isomerizing hexenolysis.

    fig. S18. Experimental chain length distributions; MCL: 12.9; 14.4; 17.5.

    fig. S19. Simulated distributions; turnover number (TON) M = 30,000; TON I = 7500; MCL: 10.3; 13.8; 17.3.

    fig. S20. Simulated distributions; TON M = 30,000; TON I = 15,000; MCL: 10.4; 13.7; 16.8.

    fig. S21. Simulated distributions; TON M = 30,000; TON I = 30,000; MCL: 10.5; 13.5; 16.4.

    fig. S22. Simulated distributions; TON M = 20,000; TON I = 5,000; MCL: 10.2; 13.8; 17.5.

    fig. S23. Simulated distributions; TON M = 40,000; TON I = 10,000; MCL: 10.3; 11.7; 15.1.

    fig. S24. Mass-corrected gas chromatogram of the mixture obtained by sequential isomerizing ethenolysis.

    fig. S25. Additional Ru-based metathesis catalysts tested in the isomerizing ethenolysis.

    fig. S26. Raw gas chromatograms of the product mixture obtained by single-step isomerizing ethenolysis before and after hydrogenation.

    fig. S27. Mass-corrected gas chromatogram of the product mixture obtained by single-step isomerizing ethenolysis.

    fig. S28. Boiling point curves of commercial diesel and biodiesel (RME) before and after isomerizing ethenolysis.

    fig. S29. Experimental chain length distributions; MCL: 12.3; 13.2; 15.7.

    fig. S30. Simulated distributions; TON M = 30,000; TON I = 15,000; MCL: 8.9; 12.3; 15.7.

    fig. S31. Experimental chain length distributions; MCL: 12.3; 11.8; 13.9.

    fig. S32. Simulated distributions; TON M = 15,000; TON I = 3000; MCL: 7.6; 10.6; 13.6.

    table S1. Product distributions obtained experimentally by isomerizing hexenolysis of RME.

    table S2. Equilibrium product distributions calculated for the isomerizing hexenolysis of RME.

    table S3. Comparison of product distributions obtained from isomerizing hexenolysis of RME.

    table S4. Optimization of the one-step isomerizing ethenolysis of RME.

    table S5. EN ISO 3405 distillation data of isomerizing metathesis reactions with RME.

    movie S1. Webra “Winner” 2.5-cm3 self-igniting model diesel engine operated with the fuel obtained via isomerizing ethenolysis of rapeseed methyl ester.

    data file S1. MatLab simulation.

    References (3749)

  • Supplementary Materials

    This PDF file includes:

    • Supplementary Materials and Methods
    • Supplementary Text
    • fig. S1. Ru-based metathesis catalysts tested in the isomerizing hexenolysis, including second-generation indenylidene-ruthenium complexes Umicore M41 (Ru-2) and M31 (Ru-3) and Hoveyda-type catalysts Umicore M51 (Ru-4), M72 SIMes (Ru-5), and M74 SIMes (Ru-6).
    • fig. S2. Olefin blends obtained by isomerizing hexenolysis with different Ru catalysts.
    • fig. S3. State-of-the-art isomerization catalysts tested in the isomerizing hexenolysis.
    • fig. S4. Mass-corrected GC with IC-1.
    • fig. S5. Mass-corrected GC with IC-2.
    • fig. S6. Gas chromatogram with IC-3.
    • fig. S7. Gas chromatogram with IC-4.
    • fig. S8. Mass-corrected GC with IC-5.
    • fig. S9. Mass-corrected GC with IC-6.
    • fig. S10. Mass-corrected GC with IC-7.
    • fig. S11. Mass-corrected GC with IC-8.
    • fig. S12. Mass-corrected gas chromatogram with 0 equiv 1-hexene.
    • fig. S13. Mass-corrected gas chromatogram with 0.3 equiv 1-hexene.
    • fig. S14. Mass-corrected gas chromatogram with 1 equiv 1-hexene.
    • fig. S15. Mass-corrected gas chromatogram with 1.5 equiv 1-hexene.
    • fig. S16. Calculated boiling point curves of RME product blends after isomerizing cross-metathesis with different amounts 1-hexene, along with pure RME and petrodiesel.
    • fig. S17. Boiling point curves of commercial diesel and biodiesel (RME) before and after isomerizing hexenolysis.
    • fig. S18. Experimental chain length distributions; MCL: 12.9; 14.4; 17.5.
    • fig. S19. Simulated distributions; turnover number (TON) M = 30,000; TON I = 7500; MCL: 10.3; 13.8; 17.3.
    • fig. S20. Simulated distributions; TON M = 30,000; TON I = 15,000; MCL: 10.4; 13.7; 16.8.
    • fig. S21. Simulated distributions; TON M = 30,000; TON I = 30,000; MCL: 10.5; 13.5; 16.4.
    • fig. S22. Simulated distributions; TON M = 20,000; TON I = 5,000; MCL: 10.2; 13.8; 17.5.
    • fig. S23. Simulated distributions; TON M = 40,000; TON I = 10,000; MCL: 10.3; 11.7; 15.1.
    • fig. S24. Mass-corrected gas chromatogram of the mixture obtained by sequential isomerizing ethenolysis.
    • fig. S25. Additional Ru-based metathesis catalysts tested in the isomerizing ethenolysis.
    • fig. S26. Raw gas chromatograms of the product mixture obtained by single-step isomerizing ethenolysis before and after hydrogenation.
    • fig. S27. Mass-corrected gas chromatogram of the product mixture obtained by single-step isomerizing ethenolysis.
    • fig. S28. Boiling point curves of commercial diesel and biodiesel (RME) before and after isomerizing ethenolysis.
    • fig. S29. Experimental chain length distributions; MCL: 12.3; 13.2; 15.7.
    • fig. S30. Simulated distributions; TON M = 30,000; TON I = 15,000; MCL: 8.9; 12.3; 15.7.
    • fig. S31. Experimental chain length distributions; MCL: 12.3; 11.8; 13.9.
    • fig. S32. Simulated distributions; TON M = 15,000; TON I = 3000; MCL: 7.6; 10.6; 13.6.
    • table S1. Product distributions obtained experimentally by isomerizing hexenolysis of RME.
    • table S2. Equilibrium product distributions calculated for the isomerizing hexenolysis of RME.
    • table S3. Comparison of product distributions obtained from isomerizing hexenolysis of RME.
    • table S4. Optimization of the one-step isomerizing ethenolysis of RME.
    • table S5. EN ISO 3405 distillation data of isomerizing metathesis reactions with RME.
    • Legend for movie S1
    • Legend for data file S1
    • References (37–49)

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    Other Supplementary Material for this manuscript includes the following:

    • movie S1 (.mp4 format). Webra “Winner” 2.5-cm3 self-igniting model diesel engine operated with the fuel obtained via isomerizing ethenolysis of rapeseed methyl ester.
    • data file S1 (.m format). MatLab simulation.

    Files in this Data Supplement:

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