1. Biodiesel from Waste or Unrefined Oils Using Calcium Oxide-based Catalysts
AICHe Meeting at Nov. 16 , 2008
Shuli Yan, Manhoe Kim, Steve O. Salley and K. Y. Simon Ng
National Biofuels Energy Laboratory
NextEnergy/Wayne State University
Detroit, MI 48202
Hi, thank you very much for give me this chance to introduce our work on biodiesel production catalysts in our lab. 1

2. Content Introduction Experiment Results and Discussion Conclusion
Biodiesel
Traditional Processes for Biodiesel Production
Literature Review
Experiment
Results and Discussion
Catalyst Activity
Catalyst Structure
Effect of Water and FFA in Oil Feedstock
Effect of H2O and CO2 in Air
Effect of Reaction Conditions
Transesterification Mechanism
Conclusion

3. Introduction Biodiesel A mixture of fatty acid esters
Derived from vegetable oils, animal fats, waste oils 3

4. Introduction Biodiesel - Advantages Biodegradable Low emission profile
Low toxicity
Efficiency
High lubricity 4

5. Introduction Traditional Processes for Biodiesel Production
Refined oils as feedstock (food-grade vegetable oils)
Homogeneous strong base or acid catalysts (NaOH, H2SO4)
FFA content is lower than 0.5 % (wt)
Water content is lower than 0.06% (wt)
High price
Highly corrosive
Long oil pretreatment process
Long product purification process
Large amount of waste water
Long time for phase separation
High process cost 5

6. Introduction Decrease of Feedstock Cost Decrease of Process Cost
Using inexpensive oils as feedstock
Crude vegetable oils, recycled cooking oils, trap grease etc.
Simplifying the oil pretreatment process
Simplifying the product purification process
Replace homogeneous catalysts by heterogeneous catalysts 6

7. Solid Base Catalysts Catalyst T Time(h) Conv.(%) Ref. KNO3/Al2O3 65°C7 87 1
ZnO
120°C 24 80 2
HT (Mg-Al)
180°C 92 3
SO42-/ZrO2
200°C 4
95.7
I2/Zn 96 5
Nafion acid resins
60°C 8 50 6
1. Catalytic activities of most of them are much lower than homogeneous catalysts such as NaOH.
2. Most of them were conducted at elevated temperature and pressure
3. there is little information regarding their catalytic durability.
Goal

8. Solid Base Catalysts Catalyst T Time(h) Conv.(%) Ref. Nano-CaO
Room temperature
6-24 95 10
CaO
65°C 24 93 11 3 60 12
CaO, Ca(OH)2, CaCO3
95.7 13
1. Catalytic activities much lower than NaOH.
2. Conducted at elevated temperature and pressure.
3. Low tolerant to water and FFA in feedstocks.

9. Research Goal
Develop an effective biodiesel process catalyst with high activity
Using solid catalysts to replace homogeneous NaOH
An improved property in tolerance to water and FFA
Using solid catalysts in food-grade, unrefined and waste oils.

10. Experiment
Oil Feedstock

11. Ammonia-Carbon Dioxide Precipitate Method
Experiment
Catalyst Preparation
Ca and La nitrate salts transparent solution
Stirring for 3h at 60 oC
Placing for 48h at RM
Filter and Wash
Drying for 24h at 100 oC
Calcining for 8h at 750 oC
Activation
Ethanol
3 N Ammonia; CO2, 4 vol %, each hours
Ammonia-Carbon Dioxide Precipitate Method

12. Experiment Catalyst Characterization Basic Property
Hammett indicator method;
Hammett indicator-benzene carboxylic acid titration method;
Specific surface area
Micromeritics model ASAP 2010 surface area analyzer (North Huntingdon, PA)
TG/DTG
Perkin Elmer Pyris-1 (Waltham, MA)
XRD
Rigaku RU2000 rotating anode powder diffractometer (Woodlands, TX)
FTIR
Perkin Elmer Spectrum 400 spectrometer (Waltham, MA)

13. Experiments Transesterification Product analysis
10.0 g of soybean oil and 7.6 g of methanol and 0.5 g activated catalyst
GC-MS
Karl Fischer (Water Content)
titration (Fatty Acid Content) 13

14. Catalyst Activity
Figure 1 Transesterification activities of Ca3La1, Ca1La0, Ca0La1, NaOH, and H2SO4 at 64.5 oC and 1 atm.

15. Catalyst Structure XRD
Figure 2 XRD spectra of Ca3La1 (curve 1), fresh Ca3La1 (curve 2), Ca0La1 (curve 3) and the Ca3La1 exposed to air for 30 days (curve 4).

16. Catalyst Structure
Table 3 Specific surface areas, XRD, basicity and catalytic activity of Ca1La0, Ca0La1, Ca3La1 and the Ca3La1 adsorbed water (Ca3La1-water) and Ca3La1 adsorbed FFA (Ca3La1-FFA).

17. Catalyst Structure FTIR
Figure 3 FTIR analysis of Ca3La1 (1), Ca3La1 adsorbed water (2) and Ca3La1 adsorbed FFA (3)

18. Effect of Water and FFA in Oil Feedstockb
Figure 4 Effect of water addition on transesterification..

19. Effect of Water and FFA in Oil Feedstock
Figure 5 Yield of FAME in the presence of different FFA addition.

20. Single Step Conversion of Unrefined and Waste Oilb
Figure 6 Yield of FAME using unrefined and waste oils (a) and diluted unrefined oils (b).

21. Effect of Water and FFA on Catalyst Structure
Basic Property
FTIR

22. Effect of H2O and CO2 in Air
Table 4 Effects of storage and pretreatment conditions on the catalytic activity of Ca3La1.

23. Effect of H2O and CO2 on Catalyst Structure
XRD
FTIR
Figure 7 FTIR spectra of Ca3La1 exposed to air about 3 min (1), 5 min (2), 8 min (3), 15 min (4) and 30 min (5).

24. Effect of H2O and CO2 on Catalyst Structure
TG/DTG
8 %
16 %
Figure 8 TG/DTG curves of Ca3La1 exposed to air for 12 hours.

25. Effect of Reaction Conditions
Figure 9 FAME yields with different mass ratio of catalyst to oil (a), with different mole ratio of methanol to oil (b), and with different reaction temperatures (c).

26. Effect of Reaction Conditions
Figure 9 FAME yields with different mass ratio of catalyst to oil (a), with different mole ratio of methanol to oil (b), and with different reaction temperatures (c).

27. Transesterification Mechanism
Adsorption Sites
Figure 10 FTIR spectra; (a) Ca3La1 adsorbed triglyceride (curve 1), free triglyceride (curve 2) and the fresh Ca3La1 (curve 3);

28. Transesterification Mechanism
Adsorption Sites
Figure 10 FTIR spectra;
(b) free methanol (curve 1), the Ca3La1 adsorbed methanol (curve 2) and the fresh Ca3La1 (curve 3).

29. R1: alkyl group of fatty acid
R2: alkyl esters of triglyceride
Figure 11 Schematic representation of possible mechanism for transesterification of triglyceride with methanol.

30. Conclusion
A single-step method using unrefined oils and calcium and lanthanum mixed oxides
strong base strength, large amount of basicity and high surface area
A strong interaction between Ca and La species
Highly tolerant to water and FFA in oil feedstock 30

31. Acknowledgement
Financial support of this research by the Department of Energy (DE ) and Michigan's 21st Century Job Fund program is gratefully acknowledged 31

32. Thanks!