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

2 Outline Introduction Introduction Proposed Research Proposed Research Closing Remarks 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 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 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 A two-step method to convert inexpensive oils to biodiesel Initially, an acidic catalyst (H 2 SO 4, 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 A two-step method to convert inexpensive oils to biodiesel Figure 2. Esterification of FFA with methanol in presence of catalyst Figure 1. Transesterification of triglyceride with alcohol

7 Introduction Heterogeneous catalysts 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 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 ( ), 22 (1), p. 145 Ngamcharussrivichai, C (2007). "Modified dolomites as catalysts for palm kernel oil transesterification". Journal of molecular catalysis. A, Chemical ( ), 276 (1-2), p. 24 Li, H (2006). "Transesterification of Soybean Oil to Biodiesel with Zn/I 2 Catalyst". Catalysis letters ( X), 107 (1-2), p. 25

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

10 Introduction Heterogeneous catalysts 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 o C, 12:1molar ratio of rapeseed oil to methanol, 2 % g catalyst/g oil, 8hr.

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

12 Introduction Heterogeneous catalysts 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: 1.Structural promoter 2.Electronic promoter

13 Introduction Heterogeneous catalysts Heterogeneous catalysts 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. 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. Therefore

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 Effect of La 3+ on the structural and catalytic properties of nanaoparticles Using sol-gel method to prepare lanthanum-containing nanoparticles Using sol-gel method to prepare lanthanum-containing nanoparticles La(NO 3 ) 3 transparent solution pH = 6 ~ 7 Stirring for 3h at 60 o C Placing for 48h at RM Water-bath evaporating at 90 o C Drying for 24h at 100 o C Calcining for 2h at 600 o C Grinding CH 3 CH 2 OH Me(CH 3 COO) n m H 2 O Figure 3 Process chart of the nanaoparticles

16 Effect of La 3+ on the structural and catalytic properties of nanaoparticles Material characterization 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 cm -1 Titration method, XPS, BET

17 Effect of La 3+ on the structural and catalytic properties of nanaoparticles Preliminary results 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 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 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 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 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 Process for biodiesel production based on inexpensive oils and La-containing nanoparticles Preliminary results Preliminary results ab 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 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 Goal Research content 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 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. 1.At high temperature and high pressure (200 o C and 3.8 MPa) using La-containing nanoparticles as catalyst. 2.At low temperature and atmospheric pressure (65 o C and 0.1 MPa) using La-containing nanoparticles as catalyst. 3.At low temperature and atmospheric pressure (65 o C and 0.1 MPa) using traditional homogeneous KOH as catalyst. three different technologies

26 Fuel properties of biodiesel Effect of oil species 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. 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. 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. 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. 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. 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!