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Renewable lubricants with tailored molecular architecture

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Science Advances  01 Feb 2019:
Vol. 5, no. 2, eaav5487
DOI: 10.1126/sciadv.aav5487
  • Fig. 1 Commercial and proposed routes for the production of lubricant base oils.

    (A) Industrial route for the production of PAOs synthetic lubricant base oils. (B) Proposed approach to biolubricant base oils. HAA of biomass-derived 2-alkylfuran with an aldehyde produces FL base oils. Hydrogenation of FL over Pd/C gives SFL base oils. HDO of FL over Ir-ReOx/SiO2 produces BPAOL base oils. (C) C30-FL1 yields from HAA reaction of 2-pentylfuran with lauraldehyde over various acid catalysts: 10 mmol 2-pentylfuran, 5 mmol lauraldehyde, and 0.05 mmol H+, e.g., 0.05 g of Aquivion PW98, 65°C, 6 hours. (D) Hydrogenation results of C30-FL1 to C30-SFL1 over Pd/C catalysts: 0.5 g of C30-FL1, 0.03 g of Pd/C, 6 MPa H2, 60°C, 2 hours. (E) HDO of C30-FL1 to C30-BPAOL1 over an Ir-ReOx/SiO2 catalyst: 0.3 g of C30-FL1, 0.15 g of catalyst, 5 MPa H2, 170°C, 12 hours.

  • Fig. 2 Comparison of experimental (Exp) and predicted (Sim) by molecule simulation kinematic viscosities at 40° and 100°C.
  • Table 1 Synthesis of FL and BPAOL base oils using 2-alkylfurans and aldehydes of varying molecular sizes.

    Reaction conditions: HAA reactions of 2-alkylfurans with aldehyde to FL were conducted using 0.05 g of Aquivion PW98, 10 mmol 2-alkylfuran, and 5 mmol aldehyde at 65°C for 6 hours. HDO of FL to the corresponding BPAOL over the Ir-ReOx/SiO2 catalyst was performed using 0.3 g of FL in 10 ml of cyclohexane solvent and 0.15 g of catalyst at 5 MPa H2 and 170°C for 12 hours.


    Embedded Image
    ReagentsHAA reactionHDO reaction
    EntryR1R2ProductsYield (%)ProductsYield (%)
    1Methyln-UndecylC22-FL180C22-BPAOL191
    2Ethyln-UndecylC24-FL182C24-BPAOL185
    3n-Propyln-UndecylC26-FL194C26-BPAOL187
    4n-Butyln-UndecylC28-FL189C28-BPAOL184
    5n-Pentyln-UndecylC30-FL190C30-BPAOL187
    6n-Hexyln-UndecylC32-FL189C32-BPAOL182
    7*n-Heptyln-UndecylC34-FL185C34-BPAOL183
    8n-PentylMethylC20-FL189C20-BPAOL187
    9n-Pentyln-PentylC24-FL293C24-BPAOL289
    10n-Pentyln-HeptylC26-FL291C26-BPAOL291
    11n-Pentyln-NonylC28-FL287C28-BPAOL287
    12n-Pentyl2-EthylpentylC26-FL385C26-BPAOL387
    13n-Hexyl2-EthylpentylC28-FL386C28-BPAOL382
    14n-Heptyl2-EthylpentylC30-FL288C30-BPAOL281

    *Eight hours.

    †Twelve hours.

    • Table 2 Properties of C30-FL1, SFL1, and BPAOL1 base oils compared with those of select commercial formulated lubricants.

      N/A, not applicable.

      Lubricant base oilsKV100* (cSt)KV40* (cSt)VIPP (°C)Noack volatility§
      (wt %)
      DSC oxidation
      onset Temperature (°C)
      C30-FL13.1412.91105<−6310170
      C30-SFL13.9117.92113<−6011.5154
      C30-BPAOL13.1911.84140−2113.8201
      ExxonMobil PAO44.119.0126−6618.8221
      Group II (150 N)5.330.6106−1314.5N/A

      *KV100 and KV40 are kinematic viscosities at 100° and 40°C, respectively (ASTM D445).

      †VI calculated from KV100 and KV40 (ASTM D2270).

      ‡PP (ASTM D97).

      §Volatility (ASTM D6375).

      ‖Oxidation stability (ASTM E2009, method B, 500 pis O2).

      ¶Mineral group II base oil.

      Supplementary Materials

      • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/2/eaav5487/DC1

        Scheme S1. Strategies for the synthesis of 2-alkylfurans.

        Scheme S2. Reaction pathway for HAA of 2-alkylfuran with an aldehyde over acid catalyst.

        Table S1. Properties of commercial solid acid catalysts.

        Table S2. HAA reaction of different 2-alkylfurans with aldehydes over P-SiO2.

        Table S3. Simulated kinematic viscosities and viscosity index at 40° and 100°C of C30-BPAOL lubricant base oils.

        Table S4. Reaction specifications.

        Table S5. Summary of capital and operating cost for combined production of p-xylene and lubricants.

        Table S6. Summary of capital and operating cost.

        Fig. S1. Catalysts screening for the synthesis of C30-FL1.

        Fig. S2. Effect of catalyst (Aquivion PW98) amount on the yield of C30-FL1 at low and high conversions of reactants.

        Fig. S3. Effect of reaction temperature on the production of C30-FL1.

        Fig. S4. Arrhenius plot for HAA of 2-pentylfuran with lauraldehyde over Aquivion PW98.

        Fig. S5. Time course of the HAA reaction over Aquivion PW98 catalyst.

        Fig. S6. Recyclability of Aquivion PW98.

        Fig. S7. Time course of the HAA reaction for C30-FL1 synthesis over the P-SiO2 catalyst.

        Fig. S8. Recyclability of P-SiO2 for the synthesis of C30-FL1.

        Fig. S9. Thermogravimetric profiles of P-SiO2 before and after reaction.

        Fig. S10. Hydrogenation of C30-FL1 over pretreated Pd/C.

        Fig. S11. TEM images of Pd/C before and after reaction.

        Fig. S12. Recyclability of Ir-ReOx/SiO2 for the HDO of C30-FL1.

        Fig. S13. TEM images of Ir-ReOx/SiO2 before reaction and after 5 cycles.

        Fig. S14. Effect of chain length of 2-alkylfurans on the HAA reaction rate at <25% conversion.

        Fig. S15. Effect of chain length of linear aldehydes on the formation rates of the HAA condensation products at <25% conversion.

        Fig. S16. Effect of aldehyde branching on the formation rates of the HAA condensation products at <25% conversion.

        Fig. S17. Gas chromatogram trace of C30-BPAOL1 and ExxonMobil PAO4.

        Fig. S18. Flow diagram for the production of lubricants from furfural.

        Fig. S19. Overview of cost and impact of raw materials on selling price of lubricants.

        Fig. S20. Overview of cost and impact of raw materials on selling price of lubricants.

        Fig. S21. Distribution of various costs by process.

      • Supplementary Materials

        This PDF file includes:

        • Scheme S1. Strategies for the synthesis of 2-alkylfurans.
        • Scheme S2. Reaction pathway for HAA of 2-alkylfuran with an aldehyde over acid catalyst.
        • Table S1. Properties of commercial solid acid catalysts.
        • Table S2. HAA reaction of different 2-alkylfurans with aldehydes over P-SiO2.
        • Table S3. Simulated kinematic viscosities and viscosity index at 40° and 100°C of C30-BPAOL lubricant base oils.
        • Table S4. Reaction specifications.
        • Table S5. Summary of capital and operating cost for combined production of p-xylene and lubricants.
        • Table S6. Summary of capital and operating cost.
        • Fig. S1. Catalysts screening for the synthesis of C30-FL1.
        • Fig. S2. Effect of catalyst (Aquivion PW98) amount on the yield of C30-FL1 at low and high conversions of reactants.
        • Fig. S3. Effect of reaction temperature on the production of C30-FL1.
        • Fig. S4. Arrhenius plot for HAA of 2-pentylfuran with lauraldehyde over Aquivion PW98.
        • Fig. S5. Time course of the HAA reaction over Aquivion PW98 catalyst.
        • Fig. S6. Recyclability of Aquivion PW98.
        • Fig. S7. Time course of the HAA reaction for C30-FL1 synthesis over the P-SiO2 catalyst.
        • Fig. S8. Recyclability of P-SiO2 for the synthesis of C30-FL1.
        • Fig. S9. Thermogravimetric profiles of P-SiO2 before and after reaction.
        • Fig. S10. Hydrogenation of C30-FL1 over pretreated Pd/C.
        • Fig. S11. TEM images of Pd/C before and after reaction.
        • Fig. S12. Recyclability of Ir-ReOx/SiO2 for the HDO of C30-FL1.
        • Fig. S13. TEM images of Ir-ReOx/SiO2 before reaction and after 5 cycles.
        • Fig. S14. Effect of chain length of 2-alkylfurans on the HAA reaction rate at <25% conversion.
        • Fig. S15. Effect of chain length of linear aldehydes on the formation rates of the HAA condensation products at <25% conversion.
        • Fig. S16. Effect of aldehyde branching on the formation rates of the HAA condensation products at <25% conversion.
        • Fig. S17. Gas chromatogram trace of C30-BPAOL1 and ExxonMobil PAO4.
        • Fig. S18. Flow diagram for the production of lubricants from furfural.
        • Fig. S19. Overview of cost and impact of raw materials on selling price of lubricants.
        • Fig. S20. Overview of cost and impact of raw materials on selling price of lubricants.
        • Fig. S21. Distribution of various costs by process.

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