final seminar presentation jan. 22 2014
TRANSCRIPT
Hydrodeoxygenation of Phenol Using Supported Ruthenium Catalysts
Ashley BrooksJanuary 22, 2014
Dr. Rachel Narehood Austin and Dr. Ryan Nelson Bates College, Department of Chemistry
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
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
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
Hydrodeoxygenation of Phenol
Pyrolysis oil is about 2.6% phenol and 29.7% phenolic compounds
Phenol products are easily analyzed on GCMS
OH
OHO
H2
2 H2H2
DDO
HYD
H2OH2
H2O
Our DDO catalyst process
• Strive for highly active catalysts (large % HDO) • Currently, unclear how to optimize
Design
Synthesis
TestingCharacterization
Redesign
Catalysts Generations - % Major Products
Catalyst
CalcinedRuCl3/MCM-41
9.2 6.8 3.8 72.7
CalcinedRuCl3/TiO2
26.1 2.2 17.5 54.5
UncalcinedRuCl3/TiO2
86.2 1 1 10.8
OH O
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
Hypothesis1. 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
Thesis Objective
Test hypothesis
Replicate enough to understand variability
Optimize use of ruthenium
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)
Experimental Design
RuCl3
ORRu(acac)3
CeO2
0.5%1%
1.5%3%
TiO2
0.5%1%
1.5%3%
= 32 total
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
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)
Percent Major ProductsCatalyst
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
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
Acknowledgements
Dr. R. AustinDr. M. WheelerDr. R. NelsonPamela RuizMary Lewis
Ben Goundie Cody Newman Jayme Gough
DOE Grant
`
Questions?
Ashley BrooksSenior Thesis Seminar
January 22, 2014
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
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
References • Joseph, J.;Baker, C.; Mukkamala, s.;Beis, S.; Wheeler, M.C.; Desisto, W. J.;Jensen, B.L.; Frederick, B.G.,
Chemical shifts and lifetimes for Nuclear Magnetic Resonance (NMR) Analysis of biofuels. Energy Fuels 2010, 24, 5153-5162
• Tang,T.; Yin, C.; Xiao, N.; Guo, M.; Xiao, F. Catal Lett 2009,127, 400-405 • 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.