1. Hydrodeoxygenation of Phenol Using
Supported Ruthenium Catalysts
Ashley Brooks
January 22, 2014
Dr. Rachel Narehood Austin and Dr. Ryan Nelson
Bates College, Department of Chemistry

2. Project Overview
• Convert wood waste (mostly lignin) into
usable economically viable alternative fuel
• The University of Maine, Bates and Bowdoin
College
• Seven year Department of Energy
Infrastructure Grant

3. Pyrolysis oil
Process:
• Thermal chemical conversion of
biomass (lignin, cellulose, etc..) to
bio - oil
• Rapid heating to 350 - 500°C without
oxygen
Bio-oil Composition:
• A mixture of over 300 compounds
• Energy density of 20 MJ/Kg
• 50 wt. % Oxygen
• Over time oil polymerizes
Vispute, T. P.; Zhang, H.; Sanna, A.; Xiao, R.; Huber, G. W., Renewable chemical commodity feedstocks
from integrated catalytic processing of pyrolysis oils. Science 2010, 330, 1222-1227.
Gregory, D. Howard College of Arts and Sciences Chemistry and Biochemistry.
http://howard.samford.edu/chemistry/bio.aspx?id=45097178667

4. Improving oil properties
“Upgrading”
• Goals for final fuel:
• Energy densities greater than 45 MJ/kg.
• 1% or less weight of oxygen
• Hydrodeoxygenation (HDO):
• Bio - oil put under high pressures of hydrogen as well as high temperatures
• Get about 10 wt. % of oxygen containing compounds thus far
• Heterogeneous supported catalysts are used
Biomass technology group http://www.btgworld.com/en/rtd/technologies/biofuels

5. Hydrodeoxygenation of Phenol
 Pyrolysis oil is about 2.6% phenol and 29.7% phenolic compounds
 Phenol products are easily analyzed on GCMS

6. Our DDO catalyst process
• Strive for highly active catalysts (large % HDO)
• Currently, unclear how to optimize
Design
Synthesis
TestingCharacterization
Redesign

7. Catalysts Generations- % Major Products
Catalyst
Calcined
RuCl3/MCM-41
9.2 6.8 3.8 72.7
Calcined
RuCl3/TiO2
26.1 2.2 17.5 54.5
Uncalcined
RuCl3/TiO2
86.2 1 1 10.8
Newman, C. Catalytic Activity of a Series of Supported Ru Hydrogeoxygenation Catalysts . 2011.
Controlling hydrogenation vs. direct deoxygenation in supported ruthenium hydrodeoxygenation catalysts Cody Newmana,b, Xiaobo Zhoub, Ben Goundie I.
Tyrone Ghampsonb,, Rachel A. Pollockb,, Zachery Rossa, M. Clayton Wheelerb, Robert W. Meulenberg, Rachel N.Austina, and Brian G. Frederick. under review in
Applied Catalysis A

8. Hypothesis
1. Reducible supports work well
- CeO2 and TiO2
2. Ruthenium chloride precursor is poisoning catalyst by
blocking active sites and preventing Ru3+ Ru0
Ruthenium(III) acetylacetonate
Ruthenium (III) chloride

9. Thesis Objective
Test hypothesis
Replicate enough to understand variability
Optimize use of ruthenium

10. Thesis Approach
Synthesize ruthenium catalysts on TiO2 and CeO2 varying
percent ruthenium 0.5 3% with two replicates of each
Synthesis method: Incipient Wetness Impregnation (IWI)

11. Experimental Design
RuCl3
OR
Ru(acac)3
CeO2
0.5%
1%
1.5%
3%
TiO2
0.5%
1%
1.5%
3%
= 32 total

12. New Pretreatment Approach
• Revision attempt to maximize
throughput of catalysts
• Reduce catalyst for 1.5 hours
in reactor
• Flowing H2 for 0.5 hrs then
37.4 atm H2 for 1 hr at 300°C

13. Hydrogenation via the Parr
Reactor
• 5 g of Phenol with 0.1 g of catalyst
• Temperature: 300°C
• Pressure: 44.2 atm with H2
• Reaction time: 1 hour
• Sample analyzed by GC/MS
• Catalyst analyzed by ICP
(pre & post reaction)

14. Percent Major Products
Catalyst
3% RuCl3/CeO2
(AB1231)
43.4 4.4 25.2 23.5
3% RuCl3/CeO2
(AB1232)
49.6 8.8 18.8 19.8
3% RuCl3/TiO2
(AB12315)
95.1 2.0 0.8 1.2

15. Summary
• New pretreatment approach works
• All catalysts synthesized
• Ruthenium on TiO2 yields the highest deoxygenated products and
favors benzene
• Removal of chloride in precursor may increase benzene and reduce
poisoning
• Experimental design is on track to successfully test hypothesis
To do
- ICP analysis of ruthenium loading
- GCMS analysis

16. Acknowledgements
Dr. R. Austin
Dr. M. Wheeler
Dr. R. Nelson
Pamela Ruiz
Mary Lewis
Ben Goundie
Cody Newman
Jayme Gough
DOE Grant

17. `
Questions?
Ashley Brooks
Senior Thesis Seminar
January 22, 2014

18. Data analysis
• Python
• Data was fit using a non negative least squares that was
simultaneously fit to reference spectra
• Equation to right is solved for each mass spectra

19. Heterogeneous Catalysts:
Spillover
Falconer J.l, Conner W.C. Spillover in Heterogeneous Catalysis. Chem. Rev. 1995, 759-788.
• Ruthenium nanoparticles help dissociated the hydrogen
• Hydrogen diffuses to support to reduce Ti or Ce forming
active sites

20. References
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B.G., Chemical shifts and lifetimes for Nuclear Magnetic Resonance (NMR) Analysis of biofuels.
Energy Fuels 2010, 24, 5153-5162
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• Shin, E,; Keane, M. A. Ind Eng Chem Res 2000, 39, 883-892.
• Zahmakiran, M.; Kodaira, T.; Ozkar, S.; App Cat B: Envir 2010, 96, 533-540.
• BRADSHAW, M. J. Global energy dilemmas: a geographical perspective. Geogr. J. 2010, 176, 275-
290.
• 2. Furimsky, E. Hydroprocessing challenges in biofuels production. Catalysis Today .
• 3. Lin, Y.; Huber, G. W. The critical role of heterogeneous catalysis in lignocellulosic biomass
conversion. Energy & Environmental Science 2009, 2, 68-80.
• 4. de Miguel Mercader, F.; Groeneveld, M.; Kersten, S.; Way, N.; Schaverien, C.; Hogendoorn, J.
Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery
units. Applied Catalysis B: Environmental 2010, 96, 57-66.
• 5. Furimsky, E. Catalytic hydrodeoxygenation. Applied Catalysis A: General 2000, 199, 147-190.
• 6. Yang, Y. Q.; Tye, C. T.; Smith, K. J. Influence of MoS2 catalyst morphology on the
hydrodeoxygenation of phenols. Catalysis Communications 2008, 9, 1364-1368.
• 7. Mukkamala, S.; Wheeler, M. C.; van Heiningen, A. R.; DeSisto, W. J. Formate-Assisted Fast
Pyrolysis of Lignin. Energy Fuels 2012, 26, 1380-1384.
• 8. Luo, Z.; Wang, S.; Liao, Y.; Zhou, J.; Gu, Y.; Cen, K. Research on biomass fast pyrolysis for liquid
fuel. Biomass Bioenergy 2004, 26, 455-462.