Shuli Yan 2008-02-18

1. Biodiesel production from oils containing high content of water and FFA using zinc lanthanum mixture oxides as catalyst Shuli Yan 2008-02-18

2. Outline • Introduction • Experiments • Results and Discussion • Biodiesel • Oils used in traditional processes for biodiesel production • Homogeneous catalysts for biodiesel production • Catalytic activity of Zn and La mixture oxides • Effect of FFA addition on transesterfication • Effect of water addition on transesterfication • Catalyst structure and their effects on biodiesel production

3. Introduction • Biodiesel • Biodegradable • Low emission profile • Low toxicity • Better fuel • Efficiency • High lubricity

4. Introduction Oils used in traditional processes for biodiesel production Food grade vegetable oils( soybean oil $2.03/gal, $0.27/lb) • FFA content is lower than 0.5 % (wt) • Water content is lower than 0.06% (wt) Therefore: Crude oils and yellow grease( about 50 % of food oil) • FFA content is in the range of 0.5 ~ 15 % (wt) • Water content is higher than 0.06% (wt)

6. Introduction Prices of some inexpensive materials ( Rudeck, 2000)

7. Introduction • Negative effects of FFA and water in homogeneous catalysis for biodiesel production • Saponification of FFA with alkaline catalysts • Hydrolysis of triglyceride

8. Introduction Homogeneous catalysts for biodiesel production • Difficulties in phase separation • A lot of washing water • Environmental unfriendly Therefore: Developing a heterogeneous catalyst

9. Our goal • Simultaneous transesterification and esterification • Minimizing hydorlysis and saponification • Developing a heterogeneous catalyst with high activity • Processing feedstocks with high content of FFA and water

10. Experiments • Catalyst preparation and characterization • Homogeneous-coprecipitation method using urea as precipitant Prepare a mixture solution of Zn(NO3)2 , La(NO3)3 andurea Heat to 100 oC and hold for 6 hr Stirred with magnetic stirrer Filter/unfilter Dry at 150 oC for 8 hr Use step-rise calcination method at 250 (2hr), 300 (2hr), 350 (2hr), 400 (2hr), 450 oC (8hr), Zn:La 1:0 1:1 3:1 9:1 0:1 Pure ZnO, Zn1La1, Zn3La1, Zn9La1, Pure La2O3 • SEM/EDS, XRD, XPS, FT-IR

11. Experiments • Transesterification Molar ratio of methanol to soybean oil-----------------42:1 Catalyst dosage--------------------2.3 %(wt) Stir speed----------------------------490 rpm

12. Experiments • FAME yield • Water content • FFA content Clarus 500 GC-MS, Perkin-Erlmer 831 KF Coulometer 809 KF Coulometer

13. Results and discussion • Catalytic activity of zinc lanthanum metal oxides for transesterification Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, stir speed is 490 rpm; using step-rising heat method to control the reaction temperature; heating speed is 2 oC/min, and hold at the target temperature for 1 min. Figure 1 Catalytic activity of metal oxides at different reaction temperatures

14. Results and discussion Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, stir speed is 490 rpm; Figure 2 Transesterification results of Zn3La1 at different temperatures

15. Results and discussion Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, reaction temperature is 200 oC stir speed is 490 rpm; Figure 3 Effect of catalyst composition on transesterification

16. Results and discussion • Effect of FFA addition on transesterification Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, reaction temperature is 200 oC, stir speed is 490 rpm; FFA content in refined oil: 0.02 % Figure 4 Yield of FAME in the presence of different FFA addition

17. Results and discussion Reaction conditions: 1. Acidic catalysis process, sulfuric acid amount is 3 %, molar ratio of methanol to oil is 6:1, reaction temperature is 60 oC, and reaction time is 96 hr. 2. Alkaline catalysis process, KOH amount is 1 %, molar ratio of methanol to oil is 6:1, reaction temperature is 25 oC, and reaction time is 8 hr. 3. Heterogeneously catalytic process, catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, and reaction time is 1.5 hr. Figure 5 Effect of FFA content on equilibrium yield of FAME of the transesterification processes

18. Results and discussion • Effect of water addition on transesterification Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm; Water content in refined oil is 0.0229 %, in methanol is 0.0191 %. Figure 6 Yield of FAME in the presence of different water addition

19. Results and discussion Reaction conditions: 1. Acidic catalysis process, sulfuric acid amount is 3 %, molar ratio of methanol to oil is 6:1, reaction temperature is 60 oC, and reaction time is 96 hr. 2. Alkaline catalysis process, KOH amount is 1 %, molar ratio of methanol to oil is 6:1, reaction temperature is 25 oC, and reaction time is 8 hr. 3. Heterogeneously catalytic process, catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, and reaction time is 145 min. Figure 7 Effect of water content on equilibrium yield of FAME of the transesterification processes

20. Results and discussion • Using oils containing high content of water and FFA in transesterification for biodiesel production Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm; Figure 8 Using oils containing high content of water and FFA for biodiesel production

21. Results and discussion • Effect of catalyst structure on transeseterification XRD, SEM/EDS, XPS, FT-IR • High specific surface area, multiporous structure, uniform bulk phase structure. • b. Both acidic and basic sites exist on the surface of catalyst, and they participate in the formation of FAME. • c. Active centre for transesterification (Effect of basic sites on transesterification) • Active centre for esterification (Effect of acidic sites on esterfication) • Catalytic ability of zinc lanthanum mixture oxides to hydrolysis reaction when oils containing high content of water

22. Results and discussion • SEM/EDS

25. Results and discussion • FFA Esterification in the presence of oil Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, FFA addition is about 5 %; Figure 9 TAN changes during the process using refined oil with 5 % FFA addition

26. Results and discussion Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, water content in oil is about 5.2 (wt)% catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, water content in oil is about 0.9 (wt)% Figure 10 water content changes during the processes using refined oil with 5 % water addition and without water addition

27. × × × × Results and discussion • Reaction pathway for FAME formation when using oils with a high content of FFA and water

28. Thank You