ANISOLE AND GUAIACOL HYDRODEOXYGENATION OVER MONOLITHIC Pt-Sn
CATALYSTS
Miguel Ángel González Borja, Daniel E. Resasco
School of Chemical, Biological and Materials Engineering – University of Oklahoma
MOTIVATION & APPROACH
EXPERIMENTAL CONDITIONS
THEME : ENERGY
OBJECTIVE
To produce stabilized bio-oil from biomass pyrolysis, that
can be used as a fuel or as a feed for existing oil refining
processes.
PROBLEM
Pyrolysis bio-oil is a complex mixture, which viscosity
rapidly increases with time. This is a challenge for
transportation and processing.
BIO-OIL MODEL
COMPOUNDS USED
FOR THIS STUDY
LAB SCALE
REACTION SYSTEM
SOLUTION
To perform upgrading of biomass pyrolysis products in the
vapor phase, before they are condensed into bio-oil. Thus
a stabilized mixture can be obtained.
DIRECT VAPOR-PHASE UPGRADING OF BIOMASS
PYROLYSIS PRODUCTS
Anisole
Catalytic
Upgrading
Pyrolysis
Reactor
High T
DESIRED PRODUCTS
Aromatics: benzene,
toluene, xylenes,
Gas
Condensation
Guaiacol
Reactants: Guaiacol / Anisole + Hydrogen (30:1 H2/Reactant molar ratio)
Temperature: 400°C Pressure: Atmospheric
Catalysts: Pt/Inconel, Sn/Inconel, Pt-Sn/Inconel, and Pt-Sn/CNF/Inconel Monoliths
STABILIZED
BIO-OIL
Char
Biomass
RESULTS III
Gas
CATALYST DEACTIVATION
ANISOLE
100
Reaction time
45 min
Monolith Structure
Bare Inconel surface
<1 m2/g of CNF
CNF coated surface
82 m2/g of CNF
Incorporation of Pt-Sn active metal
Carbon nanofiber
Carbon nanofiber
with Pt-Sn particles
80
Molar Percentage (%)
Cylindrical shape
Inconel Monolith
Coating with carbon nanofibers (CNF)
60
60
40
40
20
20
1.00
W/F
HIGH SURFACE AREA
CATALYTIC ACTIVITY
RESULTS II
MONOMETALLIC VS. BIMETALLIC CATALYSTS
Pt-Sn ALLOY IN BIMETALLIC CATALYSTS
HIGHER METAL DISPERSION
Bimetallic catalyst activity >
Monometallic catalysts activity
Pt-Sn ALLOY FORMATION
ACKNOWLEDGEMENTS
This work has been supported, in part, by the National Science Foundation (NSF EPSCoR Award EPS0814361 and MRINSF Grant 0923247) and the Department of Energy (DE-FG36GO88064). Miguel
Ángel González Borja thanks Dr. M. P. Ruiz, Dr. R. Jentoft, J. Brown, A. T. To, and M. Wulfers for their expert assistance in the characterization and synthesis of the monoliths.
Reaction time
45 min
0
0.00
1.00
2.00
Reaction time
125 min
80
80
60
60
40
40
20
20
0
0.00
2.00
W/F
W/F
Decrease
in benzene
production
0
0.00
2.00
W/F
CONCLUSIONS
TEMPERATURE
PROGRAMMED REDUCTION
Pt-Sn/CNF/Inconel activity >
Pt-Sn/Inconel activity
2.00
Decrease
in benzene
production
100
W/F = g cat/(g react./h). Represents size of the reactor
RESULTS I
This technique is
used to determine
the reduction
temperature of a
species under the
presence of
hydrogen
Reaction time
125 min
80
0
0.00
LOW PRESSURE DROP
100
100
STEPS FOR THE SYNTHESIS OF MONOLITHIC CATALYST WITH SUITABLE PROPERTIES
Low Surface Area Inconel Monolith
GUAIACOL
Molar Percentage (%)
MONOLITHIC CATALYST
Pt and Sn monometallic catalysts
• Single reduction temperatures.
Pt-Sn/Inconel catalysts
Single reduction temperature
• One metallic phase: a Pt-Sn alloy.
Pt-Sn/CNF/Inconel catalysts
Multiple reduction peaks.
• Broad distribution of particle size
• Presence of different alloy phases
• Presence of unalloyed metal
 Bimetallic (Pt-Sn alloy) monoliths showed higher
activity for the deoxygenation of guaiacol and anisole,
when compared to monometallic monoliths.
 Both Pt-Sn/Inconel and Pt-Sn/CNF/Inconel are able to
fully deoxygenate guaiacol and anisole.
 Coating with CNF greatly increased the surface area
of the monoliths, allowing for a higher uptake during
the active-phase incorporation.
 Deactivation of the catalyst still needs to be
improved; however, the Pt-Sn/CNF/Inconel monolith is
a promising catalyst for the upgrading of pyrolysis
bio-oil.
REFERENCES
González-Borja, M.A., Resasco, D.E. Anisole and Guaiacol Hydrodeoxygenation over Monolithic Pt-Sn Catalysts. Energy Fuels. 2011, 25, 4155-4162.
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