Hydrodeoxygenation of guaiacol as

model compound for pyrolysis oil on

noble metal catalysts
Andrea Gutierrez, Reetta Kaila,
and Outi Krause
Laboratory of Industrial Chemistry
Helsinki University of Technology
14
th
International Congress on Catalysis
Seoul 2008
Biofuels
Biomass is the only renewable
source that can meet the demand
for carbon-based liquid fuels and
chemicals
Pyrolysis
Combustion of biomass in the absence of oxygen
Flash
pyrolysis
Combustible gas (150 kg)
Pyrolysis oil (700 kg)
Char (150 kg)
1,000 kg wood
BTG - http://www.btgworld.com/2005/pdf/technologies/folder-pyrolysis.pdf
Pyrolysis oils
Higher energy density than biomass
Complex mixture (volatile and non-
volatile compounds)
High oxygen content (~ 40 wt-%)
Water content (~ 20 wt-%)
Typically less than 40 ppm sulfur
Immiscible in mineral oil
Not as stable as mineral oil
0
20
40
60
80
100
Pine Forest residue
M
a
s
s

%
Aldehydes, ketones
Acids
'Sugars'
Water
Extractives
LMM lignin
HMM lignin
Poor fuel properties
Pyrolysis - Upgrading
Wood-based bio-oils are complex mixtures
(Carboxilic acids, alcohols, ketones, carbohydrates, degraded lignin, water, etc.)
Difficult system to study
Viscosity problems
Large amount of side reactions
Solubility problems
Model compounds to simulate the behavior of bio-oils
Pyrolysis - Upgrading
Catalytic total or partial removal of oxygenates
Decarboxylation (CDO)
Thermal cracking (CRA)
Hydrodeoxygenation (HDO)
O 4H H C 4H O H C
2 8 4 2 4 8 6
+ +
S.R.A. Kersten, W.P.M. van Swaaij, L. Lefferts, K. Seshan, (2007)
In: Catalysis for renewable: From feedstock to energy production, (Eds. Centi G.,
and van Santen R. A.), pp119-145, Wiley-VCH, Weinheim, Germany.
Existing knowledge in the refinery
CoMoS/Al
2
O
3
and NiMoS/Al
2
O
3
High H
2
consumption
Upgrading - Experimental
Wood base bio-oil
Guaiacol (GUA)
Catalysts
Noble metals
- ZrO
2
supported Rh, Pd and Pt
(0.5 wt-% total metal loading)
Sulfided catalyst
- CoMo/Al
2
O
3
Experimental conditions
Batch reactors
- T= 100 and 300 C, P= 8 MPa
- 5 h
Fresh ZrO
2
-supported
Rh and Pd (T
calc.
= 700
o
C)
Assumptions
No H
2
limitation
Excess in the gas phase
Long reaction time
Vigorous agitation
ZrO
2
-supported noble
metal catalysts
0
10
20
30
40
50
60
70
80
90
100
Non-
catalytic
ZrO2 Pt PdPt Pd RhPd RhPt Rh CoMo
G
U
A

c
o
n
v
e
r
s
i
o
n

(
%
)
T= 300
o
C, 3 h
T= 100
o
C, 5 h
Remarkable effect of temperature in catalyst performance
X
GUA
> 90 % at T= 300
o
C (high risk of coke formation)
X
GUA
100 % with RhPt and Rh at T= 100
o
C
CoMo
Non-catalytic ZrO2
Rh
Pt
RhPt
GUA
Pd
RhPd
PdPt
0.00
0.05
0.10
0.15
0.20
0.25
0.30
1.0 1.2 1.4 1.6 1.8 2.0
H/C (mol/mol)
O
/
C

(
m
o
l
/
m
o
l
)
Gasoline
and
diesel
ZrO
2
-supported noble
metal catalysts
9.7 0.6 1.7 0.6 2.6 0.6 2.6 2.0 300 C
6.7 1.8 1.0 1.0 0.6 0.4 0.6 0.5 100 C
CoMo Rh RhPt RhPd Pd PdPt Pt ZrO
2
Carbon (wt-%)
Promising!
At 100 C
Main product
Noble metals: cyclohexanediols
CoMo: cyclohexanol and gaseous
sulfided compounds
Limited deoxygenation
At 300 C
Main product
Noble metals: benzene
CoMo: benzene, gaseous and liquid
sulfided compounds
Deoxygenation predominates
300 C
ZrO
2
-supported noble
metal catalysts
HDO vs. hydrogenation (HYD)
Not limited by thermodynamics
- HYD favored at low T
- HDO favored at high T
H
2
coverage of catalyst surface
H
2
equilibrium coverage decreases
with temperature
(more H
2
on the surface at low T)
HYD at 100
o
C
HDO at 300
o
C
Why different products at 100 and 300
o
C?...
Reaction scheme - Experimental
Reaction intermediates
Catalysts
Noble metals
- Rh/ZrO
2
and RhPd/ZrO
2
catalysts
Sulfided catalyst
- CoMo/Al
2
O
3
Experimental conditions
Batch reactors
- T= 100 and 300 C, P= 8 MPa
OCH
3
methoxyphenol
CH
3
toluene
OH
phenol
O
cyclohexanone
OH
cyclohexanol
Simplified reaction scheme
OCH
3
GUA
OH
OH
OH
OH
OCH
3
OCH OCH
3 3
OCH OCH
3 3
OCH
3
OCH
3
OH
OH
H
3
C
OH
CH
3
CH
3
OH
CH
3
CH
3
O
OCH
3
O
OH
OH
SH
Conclusion
Rh and RhPd promising for the upgrading of the real pyrolysis oil
RhPd cheaper catalysts than Rh
Use of low operation temperatures in the upgrading prevent coke
formation
Significant effect of temperature on activity and selectivity of the catalysts
- T = 100
o
C HYD
- T = 300
o
C HDO
Upgrading of GUA
Complicated network of reactions
- Differences in the reaction path catalyzed by the conventional sulfided CoMo
and the noble metal catalysts
Thank you!
Acknowledgements
Ms. Eeva-Maija Ryymin
Dr. Maija Honkela
Dr. Tuula-Riitta Viljava
Technical Research
Centre of Finland
Financial support
EU-project BIOCOUP
Finnish Catalysis Society
Contact information
andrea.gutierrez@tkk.fi