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-based catalysts in hydrolysis

3 Background  Biodiesel

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

5  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) Background  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)

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8  Long production process (A two-step method) Strong base Strong acid Background

9 Simultaneous transesterification and esterification Minimizing hydorlysis Background  Developing a heterogeneous catalyst with high activity processing feedstock with high FFA and water

10 Outline  Background  Literature review  Objective  Experiment  Reference Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis

11 Literature review

12  Zinc-based catalysts in transesterification Literature review Suppes et al: Zinc Oxide and zinc carbonate, 120 o C, 24hr, yield 80 % Xie et al: KF/ZnO Li et al: I 2 /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

13 Literature review  Zinc-based catalysts in esterification CatalystsEsterificaiton ReactionReference Zinc acetatepalmitic acid with isopropanol12-14 Supported zinc acetatepalmitic acid with isopropanol15-17 Zinc carboxylateglycerol with fatty acid18 Zinc oxide, Zinc Chloride glycerol with fatty acid19 Zinc carboxylateglycerol with fatty acid20

14  Zinc-based catalysts in hydrolysis Literature review 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);

15  My previous work Literature review

16  My previous work Literature review

17  My previous work Literature review

18 Outline  Background  Literature review  Objective  Experiment  Reference Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis

19  The overall objective is to develop an effective zinc-based catalyst for both transeseterification and esterification, while limiting hydrolysis of oil. Objective 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.

20 Two aspects: Objective  Confirm the reaction pathway for methyl esters production

21  Enhance the active sites on the surface of zinc-based catalysts Objective By alloying (i.e. La 2 O 3 ) Preparation conditions ─ Calcination temperature ─ Molar ratio ─ Preparation method

22 Outline  Background  Literature review  Objective  Experiment  Reference Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis

23 Experiment  Synthesis of zinc-based catalysts  Precipitation method  Zn: La = 1:0, 1:1, 3:1, 9:1, 0:1  Drying condition: 100 o C for 8 hr.  Calcining condition: 200 ~700 o C for 8hr

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

25 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.

26 Experiment  Activity test of zinc-based catalysts Temperature(100 ~ 230 o C), 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 ) At elevated temperature and pressure in a batch reactor No mass transfer limitation Reaction conditions:

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

28 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,  [2] Muniyappa PR, Brammer SC, Noureddini H. Improved conversion of plant oils and animal fates into biodiesel and co-product. Bioresour. Technol. 1996, 6,  [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,  [5] Kusdiana, D.; Saka, S. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol. 2004, 91,  [6] Saka, S.; Kusdiana, D.; Minami, E. Non-catalytic biodiesel fuel production with supercritical methanol technologies. J. Sci. Ind. Res. 2006, 65,  [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.

29 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 –  [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 –  [18] M. Adam and Szela ü g H. Ind. Eng. Chem. Res. 43, (2004),  [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] Szela ü g, H.; Macierzanka, A. Tenside Surf. Det. 2001, 38, 377.

30 Thank you!