Nanocatalysts for Wood Conversion

Michael D. Mozuch,1 Drew Braden,2 James A. Dumesic,2and Philip J. Kersten1

1Forest Products Laboratory, USDA Forest Service, Madison, WI 53726; and 2Department of Chemical and

Biological Engineering, University of Wisconsin, Madison, WI 53706

2008 International Conference on Nanotechnology for the Forest Products Industry

June 25-27, 2008

• Wood:• a versatile source of carbon structures• a renewable source of hydrogen• together (i.e. the C and H), a versatile source for

energy-rich chemicals, including biofuels

Outline

• Wood:• a versatile source of carbon structures• a renewable source of hydrogen• together (i.e. the C and H), a versatile source for

energy-rich chemicals, including biofuels

• Problem:• Recalcitrance of wood

Outline

• Wood:• a versatile source of carbon structures• a renewable source of hydrogen• together (i.e. the C and H), a versatile source for

energy-rich chemicals, including biofuels

• Problem:• Recalcitrance of wood

• Strategy:• Nanocatalysis:

Simultaneous hydrogenation/hydrolysis

Outline

BIOMASSCARBOHYDRATES

PLATFORMCHEMICALS

Biorefinery

BIOMASSCARBOHYDRATES

PLATFORMCHEMICALS

H2

H2

H2

Biorefinery: expanding the possibilities

BIOMASSCARBOHYDRATES

OOOH

HMF

BIOMASSCARBOHYDRATES

OOOH

HMF

BIOMASSCARBOHYDRATES

H2OOOH

O

Dumesic lab: Roman-Leshkov et al. 2007. Nature 447:982-985.

HMF Dimethylfuran (DMF)

High energy density,Immiscible with water,

Potential liquid fuel

BIOMASSCARBOHYDRATES

H2OOOH

GASOLINE

Dumesic lab: Huber et al. 2005. Science 308:1446-1450.

HMF

BIOMASSCARBOHYDRATES H2 alkanes, CO2

APRSUGARSand POLYOLS

Dumesic lab: Huber et al. 2003. Science 300:2075-2077.

Where do you get the hydrogen?

BIOMASSCARBOHYDRATES H2 alkanes, CO2

APR

CH2OH

OHH

HHO

OHH

OHH

CH2OH

H2

H2O

Polyols e.g.sorbitol, xylitol

Simultaneous hydrolysis/hydrogenation e.g. Sharkov 1963.

Simultaneous hydrolysis/hydrogenation(technical objective) for higher recoveries

Concept/Rationale

• Construct acid-stable nanocatalysts• Convert solid biomass to liquid• Recover catalysts by high gradient

magnetic separation• Use product stream for fuels and

chemicals

Contrasting technology: Raney nickel and ruthenium on carbon

Ferromagnetic core

Ferromagnetic core

Graphitic shell

Ferromagnetic core

Graphitic shell

Catalyst

Ferromagnetic core

Graphitic shell

Catalyst

Modifiedsurface,e.g. hydrophobic,hydrophylic,anionic, cationic etc.

Ferromagnetic core

Graphitic shell

Catalyst

Modifiedsurface,e.g. hydrophobic,hydrophylic,anionic, cationic etc.

+

+ + +

+

++

+

+

+

+

++

+

+

++

++

+

Ferromagnetic core

Graphitic shell

Catalyst

Modifiedsurface,e.g. hydrophobic,hydrophylic,anionic, cationic etc.

-

- - -

-

--

-

-

-

-

---

-

--

--

-

Ferromagnetic core

Graphitic shell

Catalyst

Modifiedsurface,e.g. hydrophobic,hydrophylic,anionic, cationic etc.

Nanoreactors

Nanoreactors

Nanoreactors

Nanoreactors

Nanoreactors

Nanoreactors

“The frontier between homogeneous and heterogeneous catalysis”

Nanoreactors

“The frontier between homogeneous and heterogeneous catalysis”

High resolution bright field transmission electron micrograph of iron oxide with ruthenium deposits.

Transmission electron image of graphite-coated metal particle in 47-77-2S

10 nm

Brightfield transmission electron micrograph of metal nanoparticlesembedded in a carbon matrix.

High resolution transmission electron micrograph of ruthenium decoratedcarbon-coated iron nanoparticles

Considerations for success

• Catalyst synthesis

• Performance in glucose hydrogenation

• Performance in wood

• Performance in recovery

Summary• Biorefinery (vision): expanding possibilities

• Paradigm shift when H2 is readily available• New options for biofuels and chemicals

• Problem: recalcitrance of wood• Hydrogen may help solve the problem

• Strategy: nanocatalysis• Accommodate the microstructure of wood• Novel properties of nanostructures• Example: Nanostructured ruthenium on core/shell

superparamagnetic nanoparticles

Acknowledgments

• Funding: USDA Forest Service

Direct conversion of wood to polyols by simultaneous hydrolysis and hydrogenation

Cooperators:• James A. Dumesic, Department of Chemical and

Biological Engineering, University of Wisconsin• Randy D. Cortright, Virent Energy Systems, Inc.

Acknowledgments• Mike Mozuch, Forest Products Laboratory,

Madison, WI

• Drew Braden, University of Wisconsin, Madison, WI

• SEM and TEM: James Beecher, Forest Products Laboratory, Madison, WI

Questions?

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