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Biodiesel production based on crude oils using zinc-based catalysts

Biodiesel production based on crude oils using zinc-based catalysts. Shuli Yan. Outline. Background Literature review Objective Experiment Reference. Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis.

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Biodiesel production based on crude oils using zinc-based catalysts

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  1. Biodiesel production based on crude oils using zinc-based catalysts Shuli Yan

  2. Outline • Background • Literature review • Objective • Experiment • Reference • Zinc-based catalysts in transesterification • Zinc-based catalysts in esterification • Zinc-basedcatalystsin hydrolysis

  3. Background • Biodiesel

  4. Background • Advantages of using biodiesel • Biodegradable • Low emission profile • Low toxicity • Better fuel • Efficiency • High lubricity

  5. Background • High production Cost • Refined vegetable oils( soybean oil $0.35/lb) • FFA content is lower than 0.5 % (wt) • Water content is lower than 0.06% (wt) • Crude oils and yellow grease( about 70 % of refined oils) • FFA content is in the range of 0.5 ~ 15 % (wt) • Water content is higher than 0.06% (wt)

  6. Strong base Strong acid Background • Long production process (A two-step method)

  7. Background • Simultaneous transesterification and esterification • Minimizing hydorlysis • Developing a heterogeneous catalyst with high activity processing feedstock with high FFA and water

  8. Outline • Background • Literature review • Objective • Experiment • Reference • Zinc-based catalysts in transesterification • Zinc-based catalysts in esterification • Zinc-basedcatalystsin hydrolysis

  9. Literature review

  10. Literature review • Zinc-based catalysts in transesterification • Suppes et al: Zinc Oxide and zinc carbonate, 120 oC, 24hr, yield 80 % • Xie et al: KF/ZnO • Li et al: I2/ZnO • Sreeprasanth et al: Fe-Zn oxides • Esterfip－H process: Al-Zn oxides The activity of catalyst is related with its basicity The activity of catalyst is related with its acidity

  11. Literature review • Zinc-based catalysts in esterification

  12. Literature review • Zinc-based catalysts in hydrolysis • Markley, K. S. In Fatty Acids, 2nd ed.; Markley, K. S., Ed.; Interscience Publishers Ltd.: London, 1961; Part 2, Chapters 8 and 9. • Hui, Y.H.; Bailey's industrial oil and fat products, 4th ed. (In Chinese); • Shu, W. Y.; Manual of oil technology; (In Chinese);

  13. Literature review • My previous work

  14. Literature review • My previous work

  15. Literature review • My previous work

  16. Outline • Background • Literature review • Objective • Experiment • Reference • Zinc-based catalysts in transesterification • Zinc-based catalysts in esterification • Zinc-based catalysts in hydrolysis

  17. Objective • The overall objective is to develop an effective zinc-based catalyst for both transeseterification and esterification, while limiting hydrolysis of oil. This zinc-based catalyst will be used directly to catalyze some crude oils which contain FFA and water in the range of 0.5 ~ 15 % for the purpose of biodiesel production.

  18. Objective • Two aspects: • Confirm the reaction pathway for methyl esters production

  19. Objective • Enhance the active sites on the surface of zinc-based catalysts • By alloying (i.e. La2O3) • Preparation conditions • Calcination temperature • Molar ratio • Preparation method

  20. Outline • Background • Literature review • Objective • Experiment • Reference • Zinc-based catalysts in transesterification • Zinc-based catalysts in esterification • Zinc-based catalysts in hydrolysis

  21. Experiment • Synthesis of zinc-based catalysts • Precipitation method • Zn: La = 1:0, 1:1, 3:1, 9:1, 0:1 • Drying condition: 100 oC for 8 hr. • Calcining condition: 200 ~700 oC for 8hr

  22. Experiment • Characterization of zinc-based catalysts • Surface composition (AES and XPS) • Bulk composition (XRD and AAS) • Surface area (BET) • Pore structure ( mercury porosimetry)

  23. Experiment • Activity test of zinc-based catalysts • Transesterification of refined oil with methanol • Esterification of oleic acid with methanol • Hydrolysis of refined oil, hydrolysis of methyl esters • Simultaneous catalysis process, i.e. using zinc catalysts in some natural crude oils, refined oil with FFA addition, refined oil with water addition, refined oil with both FFA and water addition, respectively.

  24. Experiment • Activity test of zinc-based catalysts • At elevated temperature and pressure in a batch reactor • No mass transfer limitation • Reaction conditions: Temperature(100 ~ 230 oC), Time(0 ~ 6 hr), Molar ratio of methanol to oil(3:1 ~60:1), Catalyst dosage(0 ~ 25 % wt. ), Particle size of catalyst(10 ~ 200 mesh), Stir speed (100 ~ 600 rpm )

  25. Summary • To understand the impact of bulk structure, surface structure, and the interaction between zinc oxide and support on the yield of methyl esters.

  26. References • [1] Clark S. J., Wagner L., Schrock MD. Methyl and ethyl esters as renewable fuels for diesel engines. J. Am. Oil Chem. Soc. 1984, 61, 1632-1638. • [2] Muniyappa PR, Brammer SC, Noureddini H. Improved conversion of plant oils and animal fates into biodiesel and co-product. Bioresour. Technol. 1996, 6, 19-24. • [3] Nelson, R. G., Hower, S. A. Potential feedstock supply and costs for biodiesel production. In Bioenergy’ 94, Proceedings of the Sixth National Bioenergy Conference, Reno/Sparks, NV, 1994 • [4] Canakci, M.; Gerpen, J. V. Biodiesel production from oils and fats with high free fatty acids. Trans. ASAE 2001, 44, 1429-1436. • [5] Kusdiana, D.; Saka, S. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol. 2004, 91, 289-295. • [6] Saka, S.; Kusdiana, D.; Minami, E. Non-catalytic biodiesel fuel production with supercritical methanol technologies. J. Sci. Ind. Res. 2006, 65, 420-425. • [7] Wang C.; Sun Y.; Hu L., Poly (ethylene naphthalate) formation 1. Transesterification of dimethylnaphthalate with ethylene glycol. J. Polymer. Res. 1994, 1, 131–139.

  27. References • [12] J. Chen, L. Chen, J. Appl. Polym. Sci. 73 (1999) 35–40. • [13] E. Santacesaria, F. Trulli, L. Minervini, M. Di Serio, R. Tesser, S. Contessa, J. Appl. Polym. Sci. 54 (1994) 1371–1384. • [14] C. Wang, Y. Sun, L. Hu, J. Polym. Res. 1 (1994) 131–139. • [15] R. Nava, T. Halachev, R. Rodriguez, V.M. Castano, Catal. A: Gen. 231, (2002) 131–149. • [16] R. Nava, T. Halachev, R. Rodriguez, V.M. Castano, Microporous Mesoporous, Mater. 78 (2005) 91–96. • [17] R. Aafaqi, A.R. Mohamed, S. Bhatia, J. Chem. Technol. Biotechnol. 79, (2004) 1127–1134. • [18] M. Adam and Szelaü g H. Ind. Eng. Chem. Res. 43, (2004), 7744-7753 • [19] Pouilloux, Y.; Me´tayer, S.; Barrault, J. Synthesis of Glycerol Monooctadecanoate from Octadecanoic Acid and Glycerol. Influence of Solvent on the Catalytic Properties of Basic Oxides. • C. R. Acad. Sci. Paris, Ser. IIc, Chim. 2000, 3, 589. • [20] Szelaü g, H.; Macierzanka, A. Tenside Surf. Det. 2001, 38, 377.

  28. Thank you!

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