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

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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

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