Document Text Contents
Page 1
BASED ON
THE JUNE 25-26,
2007 WORKSHOP
WASHINGTON, D.C.
A RESEARCH ROADMAP FOR MAKING
LIGNOCELLULOSIC BIOFUELS
A PRACTICAL REALITY
UNIVERSITY
OF
MASSACHUSETTS
AMHERST
SPONSORED BY:
Breaking the Chemical
and Engineering Barriers to
Lignocellulosic Biofuels:
Next Generation
Hydrocarbon Biorefineries
THE NATIONAL SCIENCE
FOUNDATION
AMERICAN CHEMICAL
SOCIETY
THE DEPARTMENT
OF ENERGY
Page 2
Publication Date: March 2008 Suggested citation for this document:
NSF. 2008. Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels: Next Generation Hydrocarbon Biorefineries.
Ed. George W. Huber, University of Massachusetts Amherst. National Science Foundation. Chemical, Bioengineering,
Environmental, and Transport Systems Division. Washington D.C. 180 p.
Page 90
Roadmap 2007 � Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels
88
changing the composition of the support may be
important here. For example, emerging methods
of “hydrophobizing” the surface may prevent water
from interacting with these sites and can be used
to reduce their leaching.
A key issue in the use of heterogeneous catalysts
for liquid-phase processing is that the catalysts can
be recycled for re-use in batch-reactor applications
or that can be regenerated readily for flow-reactor
processes. In this respect an important part of the
overall process will be pretreatment of biomass to
remove poisons and deactivators, and this removal
will require the development of new materials and
processes for effective separations.
3.7 RECOMMENDATIONS
IN SUMMARY, the following issues appear to be of
critical importance for the successful application of
liquid-phase catalytic processing of biomass-derived
compounds:
• Achieving selective transformations with
good carbon balances
• Achieving good energy balances (e.g.,
minimizing energy-intensive distillation steps)
• Controlling pathways for oxygen management
(decarbonylation versus hydrogenation)
• Controlling hydrogen management (hydrogen
production and captive use)
• Controlling carbon and coke management
• Addressing lignin utilization (heat production
versus chemical production, such as aromatics
and cyclohexanes)
• Utilizing solvent effects to achieve desired
catalyst performance, especially in multi-
phasic reactors
• Developing effective methods for feedstock
conditioning
• Developing catalysts that are tolerant to
biomass impurities (inorganics and ash,
protein-sulfur, phosphorus)
Page 91
Next Generation Hydrocarbon Biorefineries
3 . Liquid-phase Catalytic Pro c e s s i n g
of Biomass-derived Compounds
89
3.8 REFERENCES
Hydrolysis of cellulose and hemicellulose, C. E.
Wyman, S. R. Decker, M. E. Himmel,J.W. Brady, C. E.
Skopec, L.Viikari in "Polysaccharides", 2nd edition,
(Eds.: S. Dumitriu), Marcel Dekker, Inc., New York,
2005, pp. 995-1033.
Hydrothermal degradation and fractionation of
saccharides and polysaccharides, O. Bobleter in
"Polysaccharides", 2nd edition, (Eds.: S. Dumitriu),
Marcel Dekker, Inc., New York, 2005, pp. 893-937.
Barrett, C. J., J. N. Chheda, et al. (2006).“Single-
reactor process for sequential aldol-condensation
and hydrogenation of biomass-derived compounds
in water.” Appl. Catal., B 66(1-2): 111-118.
Bianchi, C. L., P. Canton, et al. (2005).“Selective
oxidation of glycerol with oxygen using mono and
bimetallic catalysts based on Au, Pd and Pt.” Catal.
Today 102-103: 203-212.
Bicker, M., D. Kaiser, et al. (2005).“Dehydration of
D-fructose of hydroxymethylfurfural in sub- and
supercritical fluids.” J. Supercrit. Fluids 36: 118-126.
Carlini, C., P. Patrono, et al. (2005).“Selective
oxidation of 5-hydroxymethyl-2-furaldehyde to
furan-2,5-dicarboxaldehyde by catalytic systems
based on vanadyl phosphate.” Appl. Catal.,A 289:
197-204.
Chaminand, J., L. Djakovitch, et al. (2004).“Glycerol
hydrogenolysis on heterogeneous catalysts.” Green
Chem. 6: 359-361.
Collins, P. and R. Ferrier “Monosaccharides.”
Monosaccharides,Wiley,West Sussex, England,
1995.
Cortright, R. D., R. R. Davda, et al. (2002).
“Hydrogen from catalytic reforming of biomass-
derived hydrocarbons in liquid water.” Nature 418:
964-967.
Dais, P. (1987).“Intramolecular hydrogen-bonding
and solvation contributions of the relative stability
of the furanose form of fructose in dimethyl
sulfoxide.” Carbohydr. Res. 169: 159-169.
Dalavoy,T., J. E. Jackson, et al. (2007). Journal of
Catalysis 246: 15-28.
Dasari, M.A., P.-P. Kiatsimkul, et al. (2005).“Low-
pressure hydrogenolysis of glycerol to propylene
glycol.” Appl. Catal.,A 281: 225-231.
Davda, R. R., J.W. Shabaker, et al. (2005).“A review
of catalytic issues and process conditions for
renewable hydrogen and alkanes by aqueous-phase
reforming of oxygenated hydrocarbons over
supported metal catalysts.” Appl. Catal., B 56: 171-
186.
D.A. Fort, R. C. Remsing, R. P. Swatloski, P. Moyna,
G. Moyna, and R. D. Rogers, Green Chem., 2007, 9,
63–69
Franks, F. (1987).“Physical Chemistry of small
carbohydrates- equilibrium solution properties.”
Pure Appl. Chem. 59(9): 1189-1202.
Gandini,A. and M. N. Belgacem (1997). “Furans in
polymer chemistry.” Prog. Polym. Sci. 22: 1203-
1379.
Halliday, G.A., R. J. Jr.Young, et al. (2003).“One-Pot,
Two-Step, Practical Catalytic Synthesis of 2,5-
Diformylfuran from Fructose.” Org. Lett. 5: 2003-
2005.
Page 180
RESEARCH ROADMAP REPORT
BASED ON THE
JUNE 25-26, 2007 WORKSHOP
WASHINGTON, D.C.
TECHNICAL WRITING
AND EDITING:
LOREN WALKER
L2W RESEARCH
AMHERST, MA
DESIGN:
LORI LYNN HOFFER
WATERLILY DESIGN
LEVERETT, MA
BASED ON
THE JUNE 25-26,
2007 WORKSHOP
WASHINGTON, D.C.
A RESEARCH ROADMAP FOR MAKING
LIGNOCELLULOSIC BIOFUELS
A PRACTICAL REALITY
UNIVERSITY
OF
MASSACHUSETTS
AMHERST
SPONSORED BY:
Breaking the Chemical
and Engineering Barriers to
Lignocellulosic Biofuels:
Next Generation
Hydrocarbon Biorefineries
THE NATIONAL SCIENCE
FOUNDATION
AMERICAN CHEMICAL
SOCIETY
THE DEPARTMENT
OF ENERGY
Page 2
Publication Date: March 2008 Suggested citation for this document:
NSF. 2008. Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels: Next Generation Hydrocarbon Biorefineries.
Ed. George W. Huber, University of Massachusetts Amherst. National Science Foundation. Chemical, Bioengineering,
Environmental, and Transport Systems Division. Washington D.C. 180 p.
Page 90
Roadmap 2007 � Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels
88
changing the composition of the support may be
important here. For example, emerging methods
of “hydrophobizing” the surface may prevent water
from interacting with these sites and can be used
to reduce their leaching.
A key issue in the use of heterogeneous catalysts
for liquid-phase processing is that the catalysts can
be recycled for re-use in batch-reactor applications
or that can be regenerated readily for flow-reactor
processes. In this respect an important part of the
overall process will be pretreatment of biomass to
remove poisons and deactivators, and this removal
will require the development of new materials and
processes for effective separations.
3.7 RECOMMENDATIONS
IN SUMMARY, the following issues appear to be of
critical importance for the successful application of
liquid-phase catalytic processing of biomass-derived
compounds:
• Achieving selective transformations with
good carbon balances
• Achieving good energy balances (e.g.,
minimizing energy-intensive distillation steps)
• Controlling pathways for oxygen management
(decarbonylation versus hydrogenation)
• Controlling hydrogen management (hydrogen
production and captive use)
• Controlling carbon and coke management
• Addressing lignin utilization (heat production
versus chemical production, such as aromatics
and cyclohexanes)
• Utilizing solvent effects to achieve desired
catalyst performance, especially in multi-
phasic reactors
• Developing effective methods for feedstock
conditioning
• Developing catalysts that are tolerant to
biomass impurities (inorganics and ash,
protein-sulfur, phosphorus)
Page 91
Next Generation Hydrocarbon Biorefineries
3 . Liquid-phase Catalytic Pro c e s s i n g
of Biomass-derived Compounds
89
3.8 REFERENCES
Hydrolysis of cellulose and hemicellulose, C. E.
Wyman, S. R. Decker, M. E. Himmel,J.W. Brady, C. E.
Skopec, L.Viikari in "Polysaccharides", 2nd edition,
(Eds.: S. Dumitriu), Marcel Dekker, Inc., New York,
2005, pp. 995-1033.
Hydrothermal degradation and fractionation of
saccharides and polysaccharides, O. Bobleter in
"Polysaccharides", 2nd edition, (Eds.: S. Dumitriu),
Marcel Dekker, Inc., New York, 2005, pp. 893-937.
Barrett, C. J., J. N. Chheda, et al. (2006).“Single-
reactor process for sequential aldol-condensation
and hydrogenation of biomass-derived compounds
in water.” Appl. Catal., B 66(1-2): 111-118.
Bianchi, C. L., P. Canton, et al. (2005).“Selective
oxidation of glycerol with oxygen using mono and
bimetallic catalysts based on Au, Pd and Pt.” Catal.
Today 102-103: 203-212.
Bicker, M., D. Kaiser, et al. (2005).“Dehydration of
D-fructose of hydroxymethylfurfural in sub- and
supercritical fluids.” J. Supercrit. Fluids 36: 118-126.
Carlini, C., P. Patrono, et al. (2005).“Selective
oxidation of 5-hydroxymethyl-2-furaldehyde to
furan-2,5-dicarboxaldehyde by catalytic systems
based on vanadyl phosphate.” Appl. Catal.,A 289:
197-204.
Chaminand, J., L. Djakovitch, et al. (2004).“Glycerol
hydrogenolysis on heterogeneous catalysts.” Green
Chem. 6: 359-361.
Collins, P. and R. Ferrier “Monosaccharides.”
Monosaccharides,Wiley,West Sussex, England,
1995.
Cortright, R. D., R. R. Davda, et al. (2002).
“Hydrogen from catalytic reforming of biomass-
derived hydrocarbons in liquid water.” Nature 418:
964-967.
Dais, P. (1987).“Intramolecular hydrogen-bonding
and solvation contributions of the relative stability
of the furanose form of fructose in dimethyl
sulfoxide.” Carbohydr. Res. 169: 159-169.
Dalavoy,T., J. E. Jackson, et al. (2007). Journal of
Catalysis 246: 15-28.
Dasari, M.A., P.-P. Kiatsimkul, et al. (2005).“Low-
pressure hydrogenolysis of glycerol to propylene
glycol.” Appl. Catal.,A 281: 225-231.
Davda, R. R., J.W. Shabaker, et al. (2005).“A review
of catalytic issues and process conditions for
renewable hydrogen and alkanes by aqueous-phase
reforming of oxygenated hydrocarbons over
supported metal catalysts.” Appl. Catal., B 56: 171-
186.
D.A. Fort, R. C. Remsing, R. P. Swatloski, P. Moyna,
G. Moyna, and R. D. Rogers, Green Chem., 2007, 9,
63–69
Franks, F. (1987).“Physical Chemistry of small
carbohydrates- equilibrium solution properties.”
Pure Appl. Chem. 59(9): 1189-1202.
Gandini,A. and M. N. Belgacem (1997). “Furans in
polymer chemistry.” Prog. Polym. Sci. 22: 1203-
1379.
Halliday, G.A., R. J. Jr.Young, et al. (2003).“One-Pot,
Two-Step, Practical Catalytic Synthesis of 2,5-
Diformylfuran from Fructose.” Org. Lett. 5: 2003-
2005.
Page 180
RESEARCH ROADMAP REPORT
BASED ON THE
JUNE 25-26, 2007 WORKSHOP
WASHINGTON, D.C.
TECHNICAL WRITING
AND EDITING:
LOREN WALKER
L2W RESEARCH
AMHERST, MA
DESIGN:
LORI LYNN HOFFER
WATERLILY DESIGN
LEVERETT, MA
