Proposal

1. Proposal Simultaneous transesterification and esterification using lanthanum-containing nanoparticles as catalyst for biodiesl production Shuli YAN 20080310

2. Outline • Introduction • Proposed Research • Closing Remarks • Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Fuel properties of biodiesel

3. Introduction • Biodiesel • a mixture of fatty acid esters of low alkyl-chain alcohols • one of the most promising substitutes for diesel engine fuels • a major barrior in the commercialization high manufacturing cost the cost of the refined oil occupy 80% of the gross cost of biodiesel

4. Introduction • Inexpensive oils • less-expensive raw materials are preferred for biodiesel production • yellow grease • crude vegetable oils • waste cooking oil Large amount of free fatty acids (FFA)

5. Introduction • A two-step method to convert inexpensive oils to biodiesel Initially, an acidic catalyst (H2SO4, HCl) is used to esterify FFA with methyl alcohol to form esters Then in the second stage an alkaline catalyst (NaOH, KOH) is used to transesterify oil. Highly corrosive Difficult to remove catalyst from the biodiesel product Deposit problems of waste water Loss of catalyst

6. Introduction • A two-step method to convert inexpensive oils to biodiesel Figure 1. Transesterification of triglyceride with alcohol Figure 2. Esterification of FFA with methanol in presence of catalyst

7. Introduction • Heterogeneous catalysts Non- corrosive easy to remove catalyst from the biodiesel product No waste water Regeneration of catalyst Development of a heterogeneous catalyst that is active in both transesterification and esterification reaction is crucial for decreasing the biodiesel manufacturing cos

8. Introduction • Heterogeneous catalysts using Mg, Ca and Zn inorganic compounds in transesterification • Li, E (2008). "Transesterification of Vegetable Oil to Biodiesel over MgO-Functionalized Mesoporous Catalysts". Energy & fuels (0887-0624), 22 (1),p. 145 • Ngamcharussrivichai, C (2007). "Modified dolomites as catalysts for palm kernel oil transesterification". Journal of molecular catalysis. A, Chemical (1381-1169), 276 (1-2),p. 24 • Li, H (2006). "Transesterification of Soybean Oil to Biodiesel with Zn/I2 Catalyst". Catalysis letters (1011-372X), 107 (1-2),p. 25

9. Introduction • Heterogeneous catalysts The catalytic activity is rather low Due to the large crystal size of active compounds Nanostructural compounds offer higher surface area, smaller crystal size and higher number of basic sites for transesterification. In this research, nanopowder of Mg, Ca and Zn inorganic compounds is proposed to improve the transesterification results

10. Introduction • Heterogeneous catalysts Our previous works Fig. 3 Catalytic activities of homogeneous catalyst NaOH, CaO, MgO, and a binary alkaline earth metal oxides. Reaction conditions: 64.5 oC, 12:1molar ratio of rapeseed oil to methanol, 2 % g catalyst/g oil, 8hr .

11. Introduction • Heterogeneous catalysts Our previous works Fig. 4 Effects of water and FFA on the equilibrium conversion ratio Reaction conditions: 64.5 oC, 12:1molar ratio of rapeseed oil to methanol, 2 % g CaO catalyst/g oil, 8hr .

12. Introduction • Heterogeneous catalysts Lanthanum shows some activity in other esterification reactions Small addition of La can improve both basic and acid sites on the surface of nano metal oxides • Lanthanum acts as: • Structural promoter • Electronic promoter

13. Introduction • Heterogeneous catalysts Therefore In this research, immobilization of La on nanopowder of Mg, Ca and Zn metal oxides is suggested to be beneficial to simultaneous transesterification of oil and esterification of FFA for the purpose of biodiesel production. The goal of this research is to prepare La-modified nanopowder of Mg, Ca and Zn inorganic compounds, and use them as catalyst in converting inexpensive oils into biodiesel.

14. Proposed Research • Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Fuel properties of biodiesel

15. La(NO3)3 transparent solution pH = 6 ~ 7 Me(CH3COO)nmH2O CH3CH2OH Stirring for 3h at 60 oC Placing for 48h at RM Water-bath evaporating at 90 oC Drying for 24h at 100 oC Calcining for 2h at 600 oC Grinding Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Using sol-gel method to prepare lanthanum-containing nanoparticles Figure 3 Process chart of the nanaoparticles

16. Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Material characterization XRD patterns are taken with a Rigaku RU2000 rotating anode powder diffractometer equiped with CuKα radiation (40kV, 200mA). SEM images are taken with a Scanning Electron Microscope (Hitachi S-2400) from the calcined samples. The composition of the catalyst is measured by the SEM equipped with EDS. Maximum operating high voltage is 25kV. FTIR are recorded on Spectrum Spotlight 200™. Accumulate 128 scans at a resolution of 2 cm-1 in the range of 400-4000 cm-1 Titration method, XPS, BET

17. Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Preliminary results Figure 4 SEM of ZnO nanoparticles containing La

18. Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Preliminary results Figure 5 Catalytic activities of ZnO nanoparticles containing La

19. Effect of La 3+ on the structural and catalytic properties of nanaoparticles • Future works Manipulation of hydrolysis of acetate salts and calcination stages in catalyst preparation process, for the purpose of controling epitaxial growth of lanthanum-doped metal oxides to prepare nanaocatalysts. Crystal structure, morphology of nanoparticles, thermal decomposition behavior of La-containing xerogel, and the surface basic and acid properties of nanocatalysts will be studied and correlated with their catalytic abilities in transesterification and esterification.

20. Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Goal Design an environmentally friendly and low-cost technology for biodiesel production using La-containing nanoparticles as catalyst and inexpensive oils as oil feedstock.

21. Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Research content As nanostructured catalysts have an enhanced activity in comparison with general catalyst powders, it becomes important to investigate the effects of reaction parameters on transesterification and esterification reactions using La-containing nanocatlaysts. • Reaction temperature • Reaction time • Catalyst dosage • Molar ratio of methanol to oil

22. a b Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Preliminary results Figure 6 Transesterification results of Zn3La1 at different temperatures a: transesterification curves b: initial reaction rate

23. Process for biodiesel production based on inexpensive oils and La-containing nanoparticles • Outcomes • A technology for biodiesel production using La-containing nanoparticles as catalyst and inexpensive oils as oil feedstock will be built up. • Kinetic models for transesterification and esterification reactions will be determined. • Reaction mechanisms of transesterification and esterification on the surface of La-containing nanoparticles will be proposed.

24. Fuel properties of biodiesel • Goal • Research content Investigate the fuel properties of different biodiesels made using this new technology fuel composition, lower heating value, kinetic viscosity, specific gravity, density, water, carbon, hydrogen, oxygen, sulfur, boiling point, flash point, cloud point, pour point, cetane number etc

25. Fuel properties of biodiesel • Effect of production technology As fuel properties definitely define the quality of biodiesel, it is essential to study the effects of biodiesel production technology and oil species on biodiesel properties. three different technologies • At high temperature and high pressure (200 oC and 3.8 MPa) using La-containing nanoparticles as catalyst. • At low temperature and atmospheric pressure (65 oC and 0.1 MPa) using La-containing nanoparticles as catalyst. • At low temperature and atmospheric pressure (65 oC and 0.1 MPa) using traditional homogeneous KOH as catalyst.

26. Fuel properties of biodiesel • Effect of oil species the variety of fatty acid profiles has an impact on biodiesel fuel properties • food-grade soybean oil • crude soybean oil • crude palm oil • chicken fat • Lard • Tallow • yellow grease using La-containing nanoparticles as catalyst

27. Closing Remarks • This project focuses on the development of a new technology for biodiesel production. • The scope of this project encompasses synthesis and characterization of nanocatalyst, catalytic process design and fuel property test. • We have shown in our preliminary results that La-containing nanoparticles can indeed offer a much higher surface area, basicity and acidity. • The proposed nano-structured material is a very promising approach to cost-effectively produce high quality biodiesel. • This new class of nanostructured materials should have significant impacts on biomass catalyst technology to overcome the conversion efficiency barrier of biomass to biofuel.

28. Thank you!