Research Article

Homogeneous Catalytic Hydrogenation of

Bio-Oil and Related Model Aldehydes with
RuCl
2
(PPh
3
)
3
A homogeneous RuCl
2
(PPh
3
)
3
catalyst was prepared for the hydrogenation of
bio-oil to improve its stability and fuel quality. Experiments were first performed
on three model aldehydes of acetaldehyde, furfural and vanillin selected to repre-
sent the linear aldehydes, oxygen heterocyclic aldehydes and aromatic aldehydes
in bio-oil. The results demonstrated the high hydrogenation capability of this
homogeneous catalyst under mild conditions (5590 C, 1.33.3 MPa). The high-
est conversion of the three model aldehydes was over 90 %. Furfural and acetalde-
hyde were singly converted to furfuryl alcohol and ethanol after hydrogenation,
while vanillin was mainly converted to vanillin alcohol, together with a small
amount of 2-methoxy-4-methylphenol and 2-methoxyphenol. Further experi-
ments were conducted on a bio-oil fraction extracted by ethyl acetate and on the
whole bio-oil at 70 C and 3.3 MPa. Most of the aldehydes were transformed to
the corresponding alcohols, and some ketones and compounds with CC double
bond were converted to more stable compounds.
Keywords: Bio-oil, Homogeneous catalyst, Hydrogenation, RuCl
2
(PPh
3
)
3
Received: June 5, 2010; revised: July 19, 2010; accepted: August 13, 2010
DOI: 10.1002/ceat.201000229
1 Introduction
With the increasing energy and environmental crisis, renew-
able and environmentally friendly energy sources are widely
recognized as a potential solution to these problems. The use
of biomass energy has received extensive attention in the
recent years, because biomass is the only renewable resource to
be converted into liquid fuels. Bio-oil, a liquid fuel from fast
pyrolysis of lignocellulosic biomass, is one of the most promis-
ing renewable fuels to replace fossil fuels [14]. However, bio-
oil cannot be directly used in internal combustion engines due
to its poor volatility, high viscosity, corrosiveness and thermal
instability [5]. Hence, it is of great necessity to upgrade bio-oil
so as to improve its fuel properties.
Currently, bio-oil upgrading techniques mainly include hy-
drotreating [69], catalytic cracking [10, 11], and steam re-
forming [12, 13]. In these upgrading processes various hetero-
geneous catalysts have been used, including sulfided CoMo
and NiMo based catalysts, traditional HZSM-5 and HY zeo-
lites, mesoporous MCM-41 and SBA-15 catalysts, as well as
noble metal based catalysts [1, 14]. One of the major problems
of upgrading bio-oil is the fast deactivation of catalysts by coke
deposition, resulting from the poor thermal stability of bio-oil
[14, 15].
The poor stability of bio-oil is attributed to the presence of
many unstable compounds caused by various polymerization/
condensation reactions. Aldehydes are the most unstable com-
pounds because they can react with phenolic compounds to
form resins, with alcohols to form hemiacetals or acetals, with
water to form hydrates, with both to form oligomers [16].
These polymerization/condensation reactions would be accel-
erated with increasing temperature, leading to low yield of
upgraded oil, high production of tar, char and coke, as well as
catalyst deactivation and reactor clogging. The catalytic up-
grading of bio-oil with heterogeneous catalysts usually requires
a high reaction temperature, at least 200 C or more. At such a
high temperature, the bio-oil would rapidly form coke by
polymerizing. Therefore, it is essential to convert the aldehydes
to more stable compounds.
Homogeneous catalysts, differing greatly from hetero-
geneous catalysts, can exhibit high catalytic capabilities and
high mass transfer efficiency even under very mild conditions
[1719]. Homogeneous catalysis offers a great potential for
catalytic upgrading of bio-oil to avoid or slow down catalyst
www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 12, 20822088
Feng Huang
1
Wenzhi Li
1
Qiang Lu
1
Xifeng Zhu
1
1
Anhui Province Key Laboratory
of Biomass Clean Energy,
University of Science and
Technology of China, Hefei,
China.

Correspondence: Dr. W. Li (liwenzhi@ustc.edu.cn), Anhui Province Key

Laboratory of Biomass Clean Energy, University of Science and
Technology of China, Hefei 230026, China.
2082
deactivation by coke deposition. Mahfud et al. initially em-
ployed a homogeneous catalyst to hydrogenate two bio-oil
model compounds (acetol and hydroxyacetaldehyde), and
found that the hydroxyacetaldehyde could be effectively con-
verted at a temperature lower than 90 C and a pressure lower
than 45 bar [20].
In this study, a homogeneous RuCl
2
(PPh
3
)
3
catalyst is pre-
pared and used for the catalytic hydrogenation of three model
aldehydes, a bio-oil fraction extracted by ethyl acetate, and the
whole bio-oil. RuCl
2
(PPh
3
)
3
is selected due to its significant
catalytic performance on aldehyde and ketone hydrogenation
in a single phase system [18, 21]. Acetaldehyde, furfural, vanil-
lin are used as model compounds to represent the linear alde-
hydes, oxygen heterocyclic aldehydes and aromatic aldehydes
in bio-oil. The ethyl acetate soluble bio-oil fraction is chosen
to contain a large amount of high reactive aldehydes and phe-
nols [22]. This paper mainly focuses on the hydrogenation
effects of this homogeneous catalyst and on the influence of
reaction conditions on catalyst performance. Catalyst recycle is
not considered in this work.
2 Experimental
2.1 Chemicals
RuCl
3
3H
2
O, furfural, furfuryl alcohol and vanillin (analytical
reagents (AR)), and vanillyl alcohol (97 %) are purchased from
Aladdin (China). 2-Methoxy-4-methylphenol (98 %) is ob-
tained from Alfa Aesar. Benzaldehyde, ethyl acetate, PPh
3
,
2-methoxyphenol and acetaldehyde (40 %, AR) are purchased
from Sinopharm Chemical Reagent Co. Ltd. All chemicals are
used without further purification.
The bio-oil is produced from rice husk with an autothermal
fast pyrolysis set developed in the authors laboratory. Details
are given in [23].
2.2 Catalyst Preparation and Characterization
The RuCl
2
(PPh
3
)
3
catalyst is synthesized according to [24, 25].
Two solutions of PPh
3
(0.6 g) in methanol (15 mL) and
RuCl
3
3H
2
O (0.1 g) in methanol (10 mL) are prepared. The
PPh
3
solution is added dropwise to the RuCl
3
3H
2
O solution
with stirring. Afterwards, the mixture is refluxed at 80 C for
4 h. All the processes are operated under N
2
atmosphere. The
resulting reddish brown crystals are washed first with metha-
nol and then with diethyl ether, and finally dried under vacu-
um to obtain the RuCl
2
(PPh
3
)
3
catalyst.
The elemental analysis of the catalyst is conducted by using
an Elementar Vario EL III analyzer. The C and H contents are
determined to be 67.49 wt-% and 4.823 wt-%, similar to the
theoretical values of 67.64 wt-% and 4.697 wt-%.
2.3 Extraction of Bio-Oil with Ethyl Acetate
Bio-oil (2 g) is added to ethyl acetate (25 mL) under vigorous
stirring at room temperature. The resulting turbid, brown
mixture is centrifuged at 12 000 rpm for 15 min. The insoluble
part such as colloid is adhesive to glass walls. The brown trans-
parent top layer is separated from the residue by filter paper
and used as a substrate for the hydrotreating reaction.
2.4 Experimental Procedure
During the experiments of the model compounds, ethyl ace-
tate (20 mL), the model compound (0.002 mol) and the
RuCl
2
(PPh
3
)
3
catalyst (60 mg) are filled into a 60-mL auto-
clave (substrate/catalyst = 32 mol mol
1
, initial substrate con-
centration C
0
= 0.1 mol L
1
). The air in the autoclave is driven
out by hydrogen. Afterwards, the reactor is pressurized with
H
2
gas to the pre-established pressure and heated to the pre-set
temperature. The stirring speed of the electric rotating mixer is
at 500 rpm. During the whole reaction process, the tempera-
ture is regulated and controlled by an automatic temperature
controller, and the pressure is monitored by a pressure sensor.
After the reaction, the autoclave is cooled to room tempera-
ture, and the gases are discharged and collected for further
analysis.
During the experiments of the bio-oil fraction, 20 mL ethyl
acetate soluble fraction of bio-oil and 60 mg RuCl
2
(PPh
3
)
3
are
placed in the autoclave. The reaction is conducted at 70 C and
3.3 MPa for 3 h. During the experiments on the whole bio-oil,
7.5 mL bio-oil, 22.5 mL methanol and 0.1 mmol RuCl
2
(PPh
3
)
3
are placed in the autoclave. The reaction is conducted at 70 C
and 90 C, the other procedures are the same as described
above.
2.5 Product Analysis
The products are analyzed by gas chromatography (GC-1690,
KeXiao, China) with a FIDdetector. The separation is performed
with the fused-silica capillary column OV1701 (30 m 0.25 mm
0.25 lm). The injector temperature is 250 Cin the split mode.
Nitrogen is the carrier gas. The temperature program ranges
from 40 C to 250 C at a heating rate of 10 Cmin
1
and then
held at 250 C for 5 min. The quantitative analysis is performed
on the following compounds by using a four-point calibration
method: furfural, furfuryl alcohol, vanillin, vanillyl alcohol,
2-methoxyphenol, and 2-methoxy-4-methylphenol. Benzalde-
hyde is used as an internal standard, and ethyl acetate is used
as the solvent. Due to its low boiling point and poor stability,
acetaldehyde is analyzed merely semi-quantitatively based on
the peak area-% on the chromatograms.
The composition of the crude and upgraded bio-oil is ana-
lyzed by gas chromatography mass spectrometry (GC/MS) by
using an Agilent model 5975C mass selective detector and an
HP-5MS capillary column (30 m 250 lm 0.25 lm). The
injector temperature is 300 C. Helium is the carrier gas. The
oven temperature program ranges from 40 C (3 min) to
180 C at a rate of 4 Cmin
1
, and then to 280 C (5 min) at a
rate of 10 Cmin
1
. The mass spectrometer is operated in EI
mode at 70 eV. Identification of chromatographic peaks is
achieved according to the NIST MS library and the literature
data of bio-oils.
Chem. Eng. Technol. 2010, 33, No. 12, 20822088 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Bio-oil 2083
3 Results and Discussion
3.1 Hydrogenation of Furfural
During the noncatalytic experiments, furfural is stable under
the reaction conditions (3 h at 70 C and 3.0 MPa H
2
), without
the formation of any products. After catalytic hydrogenation,
furfural is singly converted to furfuryl alcohol (see Eq (1)),
without detecting any other products, indicating the high se-
lectivity of this homogeneous catalyst.
O
H
O
O
OH
H
2
RuCl
2
(PPh
3
)
3
(1)
The influence of temperature, pressure, reaction time and
the addition of acetic acid on the conversion of furfural is
shown in Figs. 13. According to Fig. 1, temperature plays an
important role in furfural conversion. As the temperature
increases from 55 C to 70 C, the conversion of furfural varies
from 46.2 % to 93.1 %. However, a further increase in temper-
ature to 90 C does not show any remarkable conversion pro-
motion, indicating that the effective hydrogenation of furfural
could be performed at the temperature as low as 70 C. Com-
pared with temperature, pressure plays a less important role in
furfural conversion, as shown in Fig. 2. As the pressure
increases from 1.3 MPa to 3.3 MPa, the conversion of furfural
increases from 81.8 % to 93.6 %. Regarding the reaction time,
hydrogenation could be finished after 2 h, as can be seen from
Fig. 3. A similar result has also been reported in a previous
study using a homogeneous Ru(TMHD)
3
catalyst for the
hydrogenation of furfural [26]. In comparison with the two
catalysts, the catalyst used in this study exhibits higher catalytic
activity in furfural conversion.
Bio-oil contains abundant carboxylic acids, acetic acid in
particular. The effect of acetic acid on furfural conversion is
investigated (see Fig. 3). Furfural conversion is accelerated in
the presence of acetic acid. The conversion of furfural amounts
to as high as 88 % after 30 min reaction compared with only
60.5 % without acetic acid. What accounts for this might be as
follows: the RuCl
2
(PPh
3
)
3
catalyst could be transformed to
complex [Ru(O
2
CCH
3
)
2
(PPh
3
)
3
] 2CH
3
CO
2
H by exchange
reaction in the presence of acetic acid [27]. This Ru acetate
species has been confirmed to be an efficient hydrogenation
catalyst in a previous study [28], and it might also have high
catalytic activity on the hydrogenation of furfural.
3.2 Hydrogenation of Vanillin
Similar to furfural, vanillin is stable in the noncatalytic pro-
cess. After catalytic hydrogenation, vanillin is mainly converted
to vanillin alcohol, together with a small amount of 2-meth-
www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 12, 20822088
Figure 1. Effect of temperature on conversion of furfural. Con-
ditions: P= 2.3 MPa, reaction time = 3 h, substrate/catalyst =
32 mol mol
1
, C
0
= 0.1 mol L
1
.
Figure 2. Effect of pressure on conversion of furfural. Con-
ditions: T = 70 C, reaction time = 3 h, substrate/catalyst =
32 mol mol
1
, C
0
= 0.1 mol L
1
.
Figure 3. Conversion of furfural in the presence and absence of
acetic acid. () C
HOAc
= 0, () C
HOAc
= 0.1 mol L
1
. Conditions:
T = 70 C, P = 2.3 MPa, substrate/catalyst = 32 mol mol
1
, C
0
=
0.1 mol L
1
.
2084 F. Huang et al.
oxy-4-methylphenol and 2-methoxyphenol (see Eq (2)). The
products vanillin alcohol and 2-methoxy-4-methylphenol
should be formed through direct hydrogenation and the
hydrodeoxygenation process, respectively. However, the forma-
tion of the product 2-methoxyphenol includes a CC cracking
process. To the best of the authors knowledge, none of the
previous studies have reported the CC cracking capability of
this homogeneous catalyst. To confirm whether the cracking
reactions take place, the gas products are collected and ana-
lyzed. A small quantity of CO
2
is detected. Hence, 2-methoxy-
phenol might result from a decarbonylation reaction by the
catalyst. It is not possible to quantify the gas due to its very
low content (lower than 0.1 % in theory) and the constraint of
experimental conditions; the detailed mechanism is under in-
vestigation.
OH
OCH
3
H
2
RuCl
2
(PPh
3
)
3
OH
OCH
3
H O
OH
OCH
3
+
OH
OCH
3
OH
+
(2)
Experiments are also performed to investigate the influence
of process parameters and the effect of acetic acid on vanillin
conversion, the results are given in Figs. 47. According to
Fig. 4, the conversion of vanillin increases with temperature,
ranging from 66.4 % at 60 C to 91.8 % at 90 C. In particular,
the products 2-methoxy-4-methylphenol and 2-methoxyphe-
nol are subject to the increase in temperature, rising from
4.6 % and 1.5 % to 6.9 % and 4.8 %, respectively. However,
vanillin alcohol first increases and then decreases, the highest
yield of 80.6 % being obtained at 80 C. As shown in Fig. 5, the
product vanillin alcohol increases steadily with pressure, while
the products 2-methoxy-4-methylphenol and 2-methoxyphe-
nol are almost independent of hydrogen pressure. Reaction
time has a similar effect on the three products under hydrogen
pressure. The yield of the product vanillin alcohol increases
from 55.7 % to 79.8 % as reaction time ranges from 3 h to 10 h
(see Fig. 6). Compared with furfural, the hydrogenation of
vanillin requires the longer reaction time. It is reported that
vanillin could first transform to vanillin alcohol as an inter-
mediate and be further converted to the product 2-methoxy-4-
methylphenol through the hydrodeoxygenation process [29].
This should also be the case in the present study, since the
formation of the product 2-methoxy-4-methylphenol was
increased at the expense of the decrease of the product vanillin
alcohol under elevated reaction conditions.
Fig. 7 indicates that the addition of acetic acid also acceler-
ates the conversion of vanillin, similar to the catalytic effect on
furfural. The conversion of vanillin is 83.2 % compared with
60.3 % without acetic acid after its 3 h reaction. It is worthy to
note that only the formation of the product vanillin alcohol is
Chem. Eng. Technol. 2010, 33, No. 12, 20822088 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 4. Effect of temperature on conversion of vanillin and
yield of products. Conditions: P = 3.3 MPa, reaction time = 6 h,
substrate/catalyst = 32 mol mol
1
, C
0
= 0.1 mol L
1
.
Figure 5. Effect of pressure on conversion of vanillin and yield of
products. Conditions: T = 70 C, reaction time = 6 h, substrate/
catalyst = 32 mol mol
1
, C
0
= 0.1 mol L
1
.
Figure 6. Effect of reaction time on conversion of vanillin and
yield of products. Conditions: T = 70 C, P= 3.3 MPa, substrate/
catalyst = 32 mol mol
1
, C
0
= 0.1 mol L
1
.
Bio-oil 2085
accelerated, while the formation of the products 2-methoxy-4-
methylphenol and 2-methoxyphenol is not influenced by ace-
tic acid. The results indicate that acetic acid could only acceler-
ate the conversion of vanillin to the corresponding alcohol,
instead of affecting the hydrodeoxygenation process and crack-
ing process. The fundamental reason might be the same as
shown in Eq (1).
3.3 Hydrogenation of Acetaldehyde
Acetaldehyde is a more reactive aldehyde than furfural and
vanillin, and its hydrogenation generates ethanol as the only
product (see Eq (3)). Under the relatively mild reaction condi-
tions (70 C, 2.3 MPa and 3 h), the influence of the initial con-
centration (0.1 to 0.4 mol L
1
) on the conversion of acetal-
dehyde is studied. The results show that the residual of
acetaldehyde is less than 5 % for all experiments, indicating
that acetaldehyde is easy to be hydrogenated. As a result, no
further study under elevated reaction conditions is performed.
O
H
OH
H
2
RuCl
2
(PPh
3
)
3
(3)
3.4 Hydrogenation of Bio-Oil Fraction Extracted by
Ethyl Acetate
Before performing catalytic hydrogenation experiments on the
whole bio-oil, experiments are first conducted on the bio-oil
fraction extracted by ethyl acetate. This bio-oil fraction con-
tains almost all the volatile species in the bio-oil, without large
molecular oligomers. Hence, the compounds in this fraction
are almost all GC/MS detectable, allowing the determination
of the catalytic effects by GC/MS.
The typical ion chromatogram from the GC/MS analysis of
this fraction is shown in Fig. 8, and the major compounds are
numbered. After hydrogenation, some compounds in the orig-
inal bio-oil fraction are not affected, while others are converted
to new ones (see Fig. 8). The main changes in product are
listed in Tab. 1. All the compounds fall into seven groups, and
the changes in their contents (calculated by the relative peak
area) are given in Tab. 2.
After catalytic hydrogenation, both furfural and vanillin are
reduced considerably while furfuryl alcohol and vanillyl alco-
hol are detected as new compounds, which is inconsistent with
the above results. Moreover, glycol is detected as a new com-
pound, too, which should come from glycolal, with its peak of
covered by the solvent. In addition, some ketones are also
reduced after catalysis. For example, 1-hydroxypropan-2-one
decreases from 3.72 % to 0.73 %, and it should be converted to
1,2-propanediol increasing from 0.39 % to 3.03 %. Because of
the above catalytic effects, the aldehydes are greatly reduced
after catalysis, and so are the ketones, despite the remarkable
increase of the alcohols.
Catalytic hydrogenation also upgrades the phenolic com-
pounds by reducing the compounds with a and b carbon-car-
bon double bond; the detailed results are shown in Tab. 3. The
phenols with a-C=C side chain are almost hydrogenated, but
the phenols with b-C=C side chain are partly hydrogenated.
For example, the product 2-methoxy-4-vinylphenol decreases
from 3.55 % to 0.35 %, and it should be converted to 2-meth-
oxy-4-ethylphenol increasing from 1.38 % to 5.50 %. The
(E)-2-methoxy-4-propenylphenol decreases from 3.18 % to
0.62 %, and 2-methoxy-4-propylphenol increases from 0.26 %
to 3.77 %.
3.5 Hydrogenation of Bio-Oil
Catalytic hydrogenation experiments are carried out on the
whole bio-oil to estimate the overall performance of this
homogeneous catalyst. The GC/MS analysis of the whole bio-
oil detects similar compounds as that of the bio-oil fraction
extracted by ethyl acetate.
During the experiments, no solid char/coke products are ob-
served, showing that bio-oil would not undergo a severe ageing
reaction under these mild reaction conditions. Moreover, a
trace of gas is detected, mainly CO
2
. The formation of CO
2
might come from the acid decarboxylation or other cracking
processes. Since methanol is used as the solvent substituting
ethyl acetate for the whole bio-oil, glycolal is detected in the
crude bio-oil and converted to glycol after catalysis.
Compared with the effects of catalytic hydrogenation on the
bio-oil fraction, it is clear that this homogeneous catalyst has
weakening effects on the whole bio-oil (see Tabs. 2 and 3). The
aldehydes could not be completely converted in the whole bio-
oil even at 90 C, while they could be almost completely con-
verted at 70 C in the bio-oil fraction. Similarly, the conversion
of phenolic compounds with b-C=C side chain is about 50 %
at 90 C, compared with over 85 % for the extracted bio-oil at
70 C.
www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 12, 20822088
Figure 7. Conversion of vanillin and yield of products in the pres-
ence of acetic acid. Conditions: T = 70 C, P = 3.3 MPa, substrate/
catalyst = 32 mol mol
1
, C
0
= 0.1 mol L
1
.
2086 F. Huang et al.
4 Conclusions
A homogeneous RuCl
2
(PPh
3
)
3
catalyst was used for the hydro-
genation of bio-oil to improve its stability and quality. The
model compounds furfural and acetaldehyde were singly con-
verted to furfuryl alcohol and ethanol after hydrogenation,
while vanillin was mainly converted to vanillin alcohol, togeth-
er with small amounts of 2-methoxy-4-methylphenol and
2-methoxyphenol. The effect of reaction conditions (5590 C,
1.33.3 MPa) and the addition of acetic acid on catalyst perfor-
mance was investigated. The highest conversion of the three
model aldehydes was over 90 %. Moreover, the addition of ace-
tic acid could accelerate the conversion of the aldehydes.
Furthermore, a bio-oil fraction extracted by ethyl acetate
and the whole bio-oil were subjected to hydrogenation. Most
of the aldehydes in this fraction could be converted to the cor-
Chem. Eng. Technol. 2010, 33, No. 12, 20822088 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 8. GC/MS ion chromatograms of crude and upgraded bio-oil fraction extracted by ethyl acetate. 1: acetic acid; 2: 1-hydroxy-2-pro-
panone; 3: ethyl propionate; 4: propyl acetate; 5: glycol; 6: 1,2-propanediol; 7: trimethylhydroxysilane; 8: furfural; 9: 2-hydroxyethyl acetate;
10: acetolacetate; 11: furfuryl alcohol; 12: trans-2,5-dimethoxytetrahydrofuran; 13: cis-2,5-dimethoxytetrahydrofuran; 14: 2-methyl-2-cyclo-
pentenone; 15: butyrolactone; 16: 1,1,3-trimethoxybutane; 17: 3-methyl-1,2-cyclopentanedione; 18: 2-methoxyphenol; 19: 3-ethyl-2-hy-
droxy-2-cyclopenten-1-one; 20: 4-ethylphenol; 21: 2-methoxy-4-methylphenol; 22: 2,3-dihydrobenzofuran; 23: 2-methoxy-4-ethylphenol; 24:
2-methoxy-4-vinylphenol; 25: syringol; 26: 2-methoxy-4-allylphenol; 27: 2-methoxy-4-propylphenol; 28: vanillin; 29: 2-methoxy-4-propenyl-
phenol; 30: vanillyl alcohol.
Table 1. Corresponding components of crude and upgraded bio-oil fraction extracted by ethyl acetate.
Crude bio-oil fraction extracted by ethyl acetate In upgraded bio-oil fraction extracted ethyl acetate
No. Compound name No. Compound name
glycolal 5 glycol
2 1-hydroxypropan-2-one 6 1,2-propanediol
8 furfural 11 furfuryl alcohol
24 2-methoxy-4-vinylphenol 23 2-methoxy-4-ethylphenol
28 vanillin
21 2-methoxy-4-methylphenol
30 vanillyl alcohol
26 2-methoxy-4-allylphenol
27 2-methoxy-4-propylphenol
29 2-methoxy-4-propenylphenol
Bio-oil 2087
responding alcohols under mild conditions (70 C, 3.3 MPa).
Meanwhile, some ketones and compounds with carbon-carbon
double bond were also converted to more stable compounds.
The catalytic effect of the homogeneous catalyst on the bio-oil
fraction was a little better than that on the whole bio-oil.
In this work, a homogeneous RuCl
2
(PPh
3
)
3
catalyst was
used to upgrade the whole bio-oil, and some progress was
made. More research is needed and being done, mainly on cat-
alyst recycle. A carrier is used to heterogenize this homoge-
neous catalyst. Thus, it could be recycled like heterogeneous
catalysts. Upgrading bio-oil under mild conditions using com-
plex catalysts is likely to find application in practice only in
this way.
Acknowledgments
This research project is funded by the National Natural Science
Hi-tech R & D Program (2009AA05Z406) and by two projects
of the National Natural Science Founda-
tion of China (50876099, 50906077).
The authors have declared no conflict of
interest.
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www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 12, 20822088
Table 2. Compositions of crude and upgraded bio-oil.
Sample Acids Aldehydes Ketones Esters Alcohols Phenols Others
Crude 14.9 10.2 13.2 4.8 4.1 26.2 19.0
Extracted 14.3 9.6 9.9 5.9 3.7 23.7 25.1
1
a
11.6 0.1 6 7.9 17.2 26.9 22.7
2
a
12.1 3 10.2 5.7 10.7 29.2 21.3
2
b
11.7 0.8 9.9 5.9 12.8 29.4 19.5
1
a
upgraded extracted bio-oil from catalytic hydrogenation at 70 C
2
a
upgraded bio-oil from catalytic hydrogenation at 70 C
2
b
upgraded bio-oil from catalytic hydrogenation at 90 C
Table 3. Compositions of different phenols in crude and up-
graded bio-oil.
Sample Phenols with
a-C=C side chain
Phenols with
b-C=C side chain
Others
Crude 4.3 4.4 17.5
Extracted 4.1 4.2 15.4
1
a
0.1 0.6 26.3
2
a
1.3 2.4 25.4
2
b
0.7 2.3 26.2
1
a
upgraded extracted bio-oil from catalytic hydrogenation at
70 C
2
a
upgraded bio-oil from catalytic hydrogenation at 70 C
2
b
upgraded bio-oil from catalytic hydrogenation at 90 C
2088 F. Huang et al.