Mesoporous Catalysis for petroleum and biofuel production.

1. Mesoporous Catalysis Ben Lehtovaara1 Andrew Finkle1 1Department of Chemical Engineering (Nanotechnology), University of Waterloo, Waterloo, Ontario, Canada

2. Outline Recap of MesoporousMaterial Synthesis Introduction to Petroleum Refining Introduction to BiofuelRefining Zeolitesvs. MesoporousMaterials Biofuel Refining Using Mesoporous/Zeolite Composites MCM - 41

4. methane, ethane, propane, aromatics, cycloalkanes, alkenes, and alkynes

5. Crude oil is refined to smaller distillates and/or liquefied petroleum gas (LPG; varying ratios of propane/butane)

6. Hydrocrackingcreates smaller distillates with high temperatures and partial pressure of H2

7. Mild Hydrocracking uses lower temperatures and pressures to create smaller distillates

8. Hydrocracking uses noble metals supported on mesoporous material, aluminosilicates, or zeolites. Each with their own advantages / disadvantages.

9. Our Focus: Mesoporous CatalysisR=catalyst (i.e. noble metal)

10. Mesoporous Materials Synthesis Mesoporous (~2-50nm pores) require surfactants as templating material to achieve desired structure Formation of Micelles via Surfactant Self Assembly Controled pore size Surfactant chain length Surfactant to Silica ratio Swelling by organic additives

12. Surfactant/Si Ratio changes phase (e.g. cubic)Other factors: -Temperature -pH -nature of surfactant Swelling Agent MCM-41 Hex. Structure “Rod-like micelles”

14. Hydrolysis to create hydroxymetallates

15. Acidic catalyst such as NaF effective

17. Activity is greatest for Zeolite material (USY-1), followed by Mesoporous MCM-41, and Amorphous Silica Aluminosilicates (ASA)

18. High Activity is a result of the higher SA of the zeolite material (pore=~2-5nm)

19. Zeolites are currently the industry choice for hydrocracking

21. This leads to increased MCM-41 desirability due to:

22. Larger exposed surface area

23. Increased dispersion of catalytic sites

25. Leaves, shoots, fronds of oil palm tree

27. Pyrolysis: decomposition in absence of oxygen

28. produces gaseous hydrocarbons, coke, and bio-oil

29. Nickel on mesoporous materials improves bio-oil yield

30. Gasification: temperatures higher than 720 degrees celsius

31. produces CO, H2, CO2, and methane

32. Fischer Tropsch Synthesis converts CO and H2 into liquid hydrocarbons such as Liquid Petrolium Gas (LPG)

35. Catalyst materials synthesized via sol-gel, hydrothermal, ion-exchange and grafting methods

37. Catalytic activity is proportional to surface area

38. Palm kernel oil had a higher conversion rate then palm olein oilIncrease pore size

40. MCM-41 selective to C5+ olefin products (diesel gasoline)

41. MCM-41 lacks in catalytic activity, incorporate ZSM-5

42. Composite named CMZ

43. Mesoporous structure synthesized on surface of ZSM-5 particles

44. Microporousstructure is combined with a mesoporous material.

45. Mesostructure: MCM-41 Zeolite: ZSM-5 Composite Zeo/Meso: CMZ (0.2,0)

47. Decreased SA with increased Aluminum

48. Due to Loss of Crystallinity

49. CMZ(0.2,0.05) had highest yield and selectivity

50. More liquid fewer gas products

52. More versatile synthesis techniques that require lower T and P and shorter periods of time (Zeolites take weeks, mesoporous take days/hours)

53. Versatility in the incorporation of other materials (heteroatoms for catalysts) into their active sites (Al3+, Ti4+)

54. Currently not as effective as zeolites in fuel refining activity

55. Composite Zeo/Meso materials do improve performance

57. Characteristics of MCM-41 and CMZ materials