Upgrading of the liquid fuel from fast pyrolysis of biomass over

MoNi/c-Al
2
O
3
catalysts
Ying Xu
a,c
, Tiejun Wang
a,b,
*
, Longlong Ma
a,b
, Qi Zhang
a,b
, Wei Liang
a,c
a
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong, China
b
Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences, Guangzhou, Guangdong, China
c
Graduate School of the Chinese Academy of Sciences, Beijing, China
a r t i c l e i n f o
Article history:
Received 9 May 2009
Received in revised form 21 October 2009
Accepted 30 October 2009
Available online 30 November 2009
Keywords:
Upgrading
Fast pyrolysis
Bio-oil
Esterication
Hydrotreatment
MoNi/c-Al
2
O
3
catalyst
a b s t r a c t
The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over
MoNi/c-Al
2
O
3
catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as
a model compound to investigate the effects of Mo promoter contents and reducing temperatures of cat-
alysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffrac-
tion and temperature programmed reduction showed that the addition of Mo promoter beneted the
uniformity of nickel species and inhibited the formation of NiAl
2
O
4
spinel in the catalysts. The GC spec-
trum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic
acid (33.20%) was attained over 0.06MoNi/c-Al
2
O
3
catalysts being reduced at 873 K. This catalyst was
chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased
from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross caloric value
increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.%
to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the
acidity were considerably improved. The results of gas chromatographymass spectrometry analysis
showed that both hydrotreatment and esterication had happened over 0.06MoNi/c-Al
2
O
3
(873) catalyst
during the upgrading process.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Biomass is one of the largest primary energy resources in the
world. Wood and other forms of biomass including energy crops
and agricultural forestry wastes are some of the main available
renewable energy resources, which account for 1415% of total en-
ergy consumption [1]. As a result of the energy demand, the cost of
fossil-based fuels and disposal of waste are increasing. Biomass, as
a renewable material which has a negligible content of sulfur,
nitrogen and ash, is supposed to be very clean. The usage of bio-
mass could reduce the dependency on fossil fuels and the carbon
dioxide emissions to atmosphere due to its zero emission to envi-
ronment [2]. Therefore, intensive efforts in research and develop-
ment of biomass utilization have been made.
Biomass fast pyrolysis has aroused great attention in recent
years. However, bio-oil has deleterious properties such as high vis-
cosity, thermal instability, corrosiveness and chemical complexity,
which set up many obstacles to its applications [3,4]. The upgrading
techniques include hydrodeoxygenation [59], catalytic cracking of
pyrolysis vapours [10], emulsication [11,12], steam reforming
[13,14], extracting chemicals from bio-oils, esterication [15,16],
etc. Among these, there is more attention on hydrodeoxygenation.
But the traditional conditions for hydrotreatment of bio-oil are
rather severe which require high temperature and high hydrogen
pressure. Thus there has strong incentive to develop a novel meth-
od to improve properties of bio-oil under mild conditions.
The main objective of this work was to discuss the effects of Mo
promoter contents and reducing temperatures of catalysts on the
activity of Ni/c-Al
2
O
3
catalysts. The upgrading of raw bio-oil was
carried out over the highest activity catalyst. The properties, ele-
ment compositions and components of bio-oil were investigated
before and after upgrading.
2. Experimental method
2.1. Catalysts preparation
Stirring the mixture of Ni(NO
3
)
2
and c-Al
2
O
3
in water with the
molar radio of Ni/Al of 10/90 for 1 h and drying them at 393 K.
The catalyst of Ni/c-Al
2
O
3
was prepared after the calcinations at
0306-2619/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2009.10.028
* Corresponding author. Address: Guangzhou Institute of Energy Conversion,
Chinese Academy of Sciences, Guangzhou, Guangdong, China. Tel.: +86 020
87057751.
E-mail address: wangtj@ms.giec.ac.cn (T. Wang).
Applied Energy 87 (2010) 28862891
Contents lists available at ScienceDirect
Applied Energy
j our nal homepage: www. el sevi er. com/ l ocat e/ apenergy
723 K. The catalyst of Ni/c-Al
2
O
3
was added into (NH
4
)
2
Mo
4
O
13
(20 mg g
1
) solution. The mixture was stirred at room temperature
for 1 h, dried and calcined at 773 K for 3 h to obtain the catalysts of
0.02MoNi/c-Al
2
O
3
. By the same method the catalysts of 0.04MoNi/
c-Al
2
O
3
, 0.06MoNi/c-Al
2
O
3
, 0.08MoNi/c-Al
2
O
3
and 0.10MoNi/c-
Al
2
O
3
were prepared by adding Ni/c-Al
2
O
3
in (NH
4
)
2
Mo
4
O
13
solu-
tion with the weight radio of 40 mg g
1
, 60 mg g
1
, 80 mg g
1
and 100 mg g
1
.
0.06MoNi/c-Al
2
O
3
catalysts were reduced by mixed gas (H
2
5 vol.%, N
2
95 vol.%) at 573 K, 673 K, 773 K, 873 K and 973 K,
respectively. The catalysts of 0.06MoNi/c-Al
2
O
3
(573), 0.06MoNi/
c-Al
2
O
3
(673), 0.06MoNi/c-Al
2
O
3
(773), 0.06MoNi/c-Al
2
O
3
(873)
and 0.06MoNi/c-Al
2
O
3
(973) were attained in the same way.
2.2. Characterization of catalysts
The X-ray diffraction (XRD) patterns of the catalysts were ob-
tained using XPert Pro MPD diffract meter with a Cu Ka radiation
operated at 40 kV and 40 mA.
Hydrogen temperature programmed reduction (H
2
-TPR) studies
were carried out in a quartz tube reactor. For each TPR experiment,
0.50 g catalyst was packed into the reactor and heated in a ow of
5 vol.% H
2
/N
2
(35 mL min
1
) from 303 K to 1 023 K at a heating rate
of 5 K min
1
. Hydrogen consumption was monitored by the change
of thermal conductivity of the efuent gas stream.
2.3. Apparatus and method
All the upgrading experiments were conducted in a 250 mL
autoclave with a stirrer and water cooling coil. The schematic dia-
gram is presented in Fig. 1.
For each run, the catalyst was used by 0.50 g per 10 mL acetic
acid or bio-oil which was sampled after 2 h reaction. After the air
was displaced, the cold hydrogen pressure was raised to 3 MPa.
An automatic controller was used to control temperature and rev-
olution of the stirrer. The model reaction was carried out at 473 K.
The upgrading of raw bio-oil was carried out at 373 K.
The conversion of acetic acid was measured quantitatively by
NaOH standard solution titration. By the titration method, the
acetic acid conversion was calculated by applying the equation:
conversion = (1 V/V
0
) 100%, in which V and V
0
are the volumes
of standard NaOH solution consumed in neutralizing 0.5 mL solu-
tion sampled at the beginning and in the process of the reaction
to change the phenolphthalein indicator pink, respectively. The
products were measured by the internal standard method through
GC2010 (Shimadzu, FID, N
2
carrier gas, column: DB-1HT
30 m 0.25 mm 0.1 lm). Isoamyl acetate was chosen as the
internal standard to discuss the mechanism reaction.
2.4. Characterization of bio-oil
The water content of the bio-oil was determined by Karl Fischer
titration (ASTM D1744, GB11146-89), performed by Metrohm 787
KF Titrino. The acidity was evaluated by PHC-3C precision pH-me-
ter from Shanghai REX Instrument Factory. The elemental analysis
was carried out with various EL Elemental Analyzer. The composi-
tion of bio-oil was detected by Shimadzu GCMS-QP2010. The sep-
aration was detected on a column of DB-5MS, 30 m 0.25 mm
0.1 lm, and the oven temperature program was 313 K (holding
for 8 min) at an average heating rate of 6 K min
1
to 553 K (holding
for 30 min).
3. Results and discussion
3.1. The activity of the catalysts
Fig. 2 shows the activity of MoNi/c-Al
2
O
3
with different Mo pro-
moter contents. Adding the assistant of Mo, the activity of catalyst
was improved obviously. The conversion of acetic acid reached
16.30% over the catalyst of 0.06MoNi/c-Al
2
O
3
. Lei and Shi [17]
found that adding the assistant of Mo to nickel-based catalysts
can promote the stability and make it more active. From Fig. 2,
the same result was gotten. In this paper, the catalyst of
0.06MoNi/c-Al
2
O
3
had the highest activity in MoNi/c-Al
2
O
3
cata-
lysts, therefore it was chosen for further investigation.
The results of 0.06MoNi/c-Al
2
O
3
activity reduced at different
temperatures were shown in Fig. 3. As it can been seen from Figs.
2 and 3, each reduced catalyst was more active than the corre-
sponding catalyst without reduction. With increasing of the reduc-
ing temperature, the activity of catalysts has increased. Among
these catalyst, the catalyst of 0.06MoNi/c-Al
2
O
3
(873) exhibited
the highest activity, while the conversion of acetic acid could reach
Heater
Controller
Cool water
P
H
2
Reactor
Electrical machine
Cool water
Thermocouple
Fig. 1. Schematic diagram of experimental apparatus.
A B C D E F G
0
2
4
6
8
10
12
14
16
18
C
o
n
v
e
r
s
i
o
n

o
f

A
c
e
t
i
c

a
c
i
d
T=473K, P 3MPa, t 2h
A- No catalyst; B- Ni/-Al
2
O
3
; C- 0.02MoNi/-Al
2
O
3
; D- 0.04MoNi/-Al
2
O
3
;
E-0.06MoNi/-Al
2
O
3
; F-0.08MoNi/-Al
2
O
3
; G- 0.10MoNi/-Al
2
O
3
Fig. 2. Effect of Mo promoter contents on catalytic activity.
Y. Xu et al. / Applied Energy 87 (2010) 28862891 2887
33.20%. After the reducing temperature reached to 873 K, the trend
changed instead.
Ni catalyst, as a good hydrotreating catalyst, is always used in
upgrading gasoline [18] or other aldehydes [19]. Besides the high
activity on hydrotreating ketones, it can promote hydrotreating
of organic acid. The activity was evaluated through the acetic acid
conversion. Figs. 2 and 3 show that without catalyst, acetic acid
had no change under the conditions of 3 MPa hydrogen pressure
and 473 K. When the catalyst was present, the acetic acid conver-
sion increased as expected. The catalyst activity was affected by
the contents of Mo promoter addition and the reducing tempera-
tures. The catalyst with 0.06 wt.% Mo addition and reduced at
873 K had the highest activity. This catalyst was chosen as the opti-
mal catalyst for upgrading of the raw fast pyrolysis bio-oil.
3.2. Mechanism of the reaction
Figs. 4a and 4b show the GC-spectrum of the model compound
before and after upgrading.
The rst peak (Rt = 5.49 min) in Fig. 4a is the characteristic peak
of acetic acid. The second one (Rt = 10.27 min) is the characteristic
peak of the internal standard (isopentyl acetate). In Fig. 4b the pin-
nacle (Rt = 5.02) was identied as the characteristic peak of ethyl
acetate. These results suggested that acetic acid was converted to
ethyl acetate through the upgrading process over the catalyst of
0.06MoNi/c-Al
2
O
3
(873).
It is reported that most of ketones and aldehydes could be re-
duced to alcohols under mild conditions over Raney nickel catalyst
[20]. In this work, the results indicated that acetic acid could be
activated to generate ethyl acetate and water in the presence of
hydrogen over the catalysts. The esterication did occur in the
reactor for the existence of ethyl acetate. Both hydrotreatment
and esterication have happened over the 0.06MoNi/c-Al
2
O
3
(873) catalyst.
3.3. X-ray diffraction analysis of catalysts
3.3.1. Different contents of Mo promoter
The X-ray diffraction (XRD) patterns of Ni/c-Al
2
O
3
catalysts
modied by different Mo contents were shown in Fig. 5.
Peaks of c-Al
2
O
3
can be seen in all diffractograms of prepared
catalysts. Characteristic peaks for NiO and NiAl
2
O
4
spinel were
more emphasized in the catalyst of Ni/c-Al
2
O
3
, but with the
increasing of Mo content, these peaks were less pronounced. When
the Mo content reached to 0.06 wt.%, the characteristic peaks of
NiO and NiAl
2
O
4
spinel were least emphasized which suggested
that nickel oxide were highly dispersed in the catalyst and the NiA-
l
2
O
4
spinel were not easy to form. Research shows that the mono-
layer dispersion threshold is affected by preparation methods, such
as the properties of supports and addition of promoters. It was re-
ported that addition of promoter in the catalyst of Ni/c-Al
2
O
3
could
increase the dispersion of NiO on the surface and inhibit the
growth of Ni grain [21]. Lei and shi [17] reported that Mo modied
Ni-B/c-Al
2
O
3
showed high thermal ability and activity for the
hydrotreatment of furfural. It was proposed that the introduction
of rare earth element could improve the thermal stability of cata-
lysts [22]. It was found that there was a strong interaction between
the catalysts and rare earth elements. The rare earth elements with
bigger atom radius inhibited the diffusion velocity of nickel atom,
reduced the accumulation of atom, and avoided the crystallization.
In this work, the addition of proper amount of Mo promoter played
Fig. 4a. GC spectrum of acetic acid before hydrotreatment.
Fig. 4b. GC spectrum of acetic acid after hydrotreatment.
10 20 30 40 50 60 70 80
f
e
d
c
b
a
Al
2
O
3
NiAl
2
O
4
NiO
Diffraction angle (2/degree)
(a) Ni/-Al2O3 (b) 0.02MoNi/-Al2O3 (c) 0.04MoNi/-Al2O3 (d) 0.06MoNi/-Al2O3
(e) 0.08MoNi/-Al2O3 (f) 0.10MoNi/-Al2O3
Fig. 5. XRD patterns of catalysts samples in different Mo content.
A B C D E
14
16
18
20
22
24
26
28
30
32
34
C
o
n
v
e
r
s
i
o
n

o
f

A
c
e
t
i
c

A
c
i
d
T=473K, P 3MPa, t 2h
A-0.06MoNi/-Al2O3(573); B-0.06MoNi/-Al2O3(673); C-0.06MoNi/-Al2O3(773);
D-0.06MoNi/-Al2O3(873); E-0.06MoNi/-Al2O3(973)
Fig. 3. Effect of reducing temperatures on catalytic activity.
2888 Y. Xu et al. / Applied Energy 87 (2010) 28862891
an equivalent role for the Mo atom radius (0.139 lm) larger than
the Ni atom radius (0.124 lm).
3.3.2. Effect of reducing temperatures on catalyst
Fig. 6 depicts the XRD patterns of 0.06MoNi/c-Al
2
O
3
catalyst at
different reducing temperatures from 573 K to 973 K.
Peaks of c-Al
2
O
3
canbe seeninall diffractograms of preparedcat-
alysts. After being reducedat the temperatures above 773 K, the NiO
diffraction peaks of the catalysts disappeared. With the increase of
reducing temperatures, the diffraction peak at 2h = 32 became pas-
sivated. Until the reducing temperature reached 973 K, there ap-
peared two peaks which belonged to Al
2
O
3
and NiAl
2
O
4
. Fig. 6
shows that the existing form of nickel species at different reducing
temperatures were different anyway. NiO diffraction peaks were
weakened but existed in the XRD patterns after being reduced from
573 K to 773 K. It showed that there was still NiO left. When the
reducing temperature was 673 K, Ni
0
being reduced from Ni
2+
was
crystallized to form ne Ni metal particles. But after the reducing
temperature reached 973 K, it was not only Ni metal but also c-
Al
2
O
3
and NiAl
2
O
4
diffraction peaks became stronger.
3.4. Temperature programmed reduction of catalysts
The reduction performance of Ni/c-Al
2
O
3
and 0.06MoNi/c-Al
2
O
3
presented two main peaks as shown in Fig. 7. The lower
temperature and more intensive peaks of H
2
-TPR prole of
0.06MoNi/c-Al
2
O
3
indicated that it could be reduced more easily
than Ni/c-Al
2
O
3
. As mentioned in literature [23], the rst peak,
between 573 K and 773 K, is most likely identied as NiO free state.
The following peak is the conversion of dispersion state of NiO to
Ni
0
. The reducing temperature of Ni species in NiAl
2
O
4
spinel is
above 1073 K which beyond the research of this paper.
The results of XRD and TPR showed that the interaction be-
tween Ni and the support of c-Al
2
O
3
catalyst was obviously weak-
ened after the addition of Mo promoter. The amount of nickel
species which could be easily reduced was increased. When the
reducing temperature was 873 K, most Ni in NiO state were re-
duced to Ni
0
and the nickel species were well dispersed, resulting
in the apparent improvement on its catalytic activity.
3.5. Upgrading of the raw fast pyrolysis bio-oil
3.5.1. Properties of bio-oil
The bio-oil properties (pH value, water content, dynamic viscos-
ity and elemental analysis) were detected before and after the
upgrading treatment (Table 1). Repeated experiments results re-
vealed that the upgrading of the raw bio-oil had a good reproduc-
ibility. The values of bio-oil properties uctuated in ranged of 3%
by the average of the repetition experiments.
MoNi/c-Al
2
O
3
catalysts are considered to have high activity of
hydrotreatment in ketone and aldehyde. If hydrotreatment on
acids and esterication had not occurred in the reactor, the water
content should not change. But as seen from Table 1, the water
content increased from 35.52 wt.% to 41.55 wt.%. The pH value of
bio-oil increased from 2.33 to 2.77. That might be the evidence that
some reactions involved acids in the raw bio-oil were promoted
over the catalyst.
The hydrogen content increased from 6.25 wt.% to 6.95 wt.%
which revealed the hydrotreatment did happen during the upgrad-
ing process. Correspondingly, the caloric value increased from
13.96 MJ/kg to 14.17 MJ/kg.
3.5.2. Composition of bio-oils
Bio-oil is a complex highly oxygenated mixture with a great
amount of macromolecules, which nearly involve all species of
oxygenated organics, such as esters, ethers, aldehydes, ketones,
phenols and organic acids. The analysis on the composition of
the raw bio-oil and upgraded one was illustrated in the spectrum
of Figs. 8a and 8b.
The bio-oil consistedinnonvolatile components, suchas furfural,
benzoic acid, benzene dicaboxylic acid, and other organic acid. Most
of the components identied were phenols and the derivatives
10 20 30 40 50 60 70 80
e
d
c
b
a
Al
2
O
3
NiAl
2
O
4
NiO
Ni
0
Diffraction angle (2/degree)
(a) 0.06MoNi/-Al2O3 (573) (b) 0.06MoNi/-Al2O3 (673) (c) 0.06MoNi/-Al2O3 (773)
(d) 0.06MoNi/-Al2O3 (873) (e) 0.06MoNi/-Al2O3 (773)
Fig. 6. XRD patterns of the catalyst samples in different reducing temperatures.
200 300 400 500 600 700 800 900 1000 1100
T/K
0.06MoNi/ -Al2O3 catalyst Ni/ -Al2O3 catalyst
Fig. 7. TPR spectra of catalysts.
Table 1
Properties and element compositions of raw bio-oil and upgraded one.
Raw bio-oil Upgraded bio-oil
I II
pH 2.33 2.77 2.75
Water content (%) 35.52 41.55 41.52
Caloric value (MJ/kg) 13.96 14.17 14.08
Element compositions (wt.%)
C 53.61 53.83 53.90
H 6.25 6.95 6.93
O 40.12 39.21 39.25
N 0.02 0.01 0.02
T = 373 K, P = 3 MPa, t = 2 h.
Y. Xu et al. / Applied Energy 87 (2010) 28862891 2889
groups attached, and nearly all of the functional groups conrmed
the existence of oxygen.
Meier et al. [20] reduced ketones and aldehydes to alcohols un-
der mild conditions over Raney nickel catalyst. Zhang et al. [15]
esteried acids to ester over solid acid catalysts. In this paper,
the evidence indicated that not only hydrotreatment, but also the
esterication have happened in the bio-oil during the upgrading
process.
The corresponding compounds which might happen in the bio-
oil are illustrated in Table 2. In the raw bio-oil, since there was no
alcohol, the ethyl acetate might be obtained as the model reaction.
Acetic acid was activated and hydrodeoxygenated to gain aldehyde,
which could be hydrotreated further to alcohol. The ethyl acetate
was obtained fromthe esterication acetic acid and alcohol. Besides
the model reaction, some other reactions happened. Acetic acid and
formaldehyde or formic acid converted to alcohols over the catalyst
under the atmosphere of hydrogen. The alcohols couldreact withor-
ganic acids to esters. In the same way, we got acetic acid, hydroxy-,
methyl ester, etc. in the upgraded bio-oil. Meanwhile 2,3-butanedi-
one was reduced to 3-hydroxy, 2-butanone.
4. Conclusions
The reduced Mo-10Ni/c-Al
2
O
3
catalyst exhibited the highest
activity in the reaction of model compound. The conversion of ace-
tic acid reached the highest point (33.2%) under the condition of
473 K and 3 MPa hydrogen pressure. Acetic acid was activated in
the atmosphere of hydrogen, and converted to ethyl acetate. The
XRD showed that Mo promoter had a promoting effect on the Ni
catalysts for the conversion of acetic acid. Furthermore, the pro-
moting effect of Mo promoter increased with its amount in the
feed until its content reached 0.06 wt.%. When the Mo content
reached 0.06 wt.%, nickel oxide was highly dispersed in the catalyst
and the NiAl
2
O
4
spinel was not easy to form. The XRD and TPR
showed that when the reducing temperature was 873 K, the free
and dispersed states were both reduced completely. When the
reducing temperature increased, it was harmful to the catalysts
for the sintered active site.
Bio-oil was upgraded over the catalyst of 0.06MoNi/c-Al
2
O
3
(873). The pH value increased from 2.33 to 2.77. The water content
increased from 35.52 wt.% to 41.55 wt.%. The caloric value in-
creased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content
of bio-oil increased from 6.25 wt.% to 6.95 wt.%. Over the
0.06MoNi/c-Al
2
O
3
(873) catalyst, both hydrotreatment and esteri-
cation have happened during the upgrading of raw bio-oil. Espe-
cially the acidity of bio-oil was decreased. Results indicate that it is
possible to improve the properties of bio-oil by hydrotreating and
esterifying carboxyl groups in the bio-oil.
Acknowledgements
The nancial support was received from the Natural Science
Foundation of China (Project Nos. 50776092 and 90610035).
Fig. 8a. GCMS spectrum of the raw fast Pyrolysis bio-oil.
Fig. 8b. GCMS spectrum of the upgraded fast Pyrolysis bio-oil.
Table 2
Corresponding components in raw and upgraded fast Pyrolysis bio-oils.
Components
in raw bio-oil In upgraded bio-oil
Acetic acid Ethanol
Formaldehyde/formic acid Methyl alcohol
Formic acid/formaldehyde Methyl formate
Acetic acid + formic acid/formaldehyde Methyl, acetic acid ester
Hydroxy, acetic acid + formic acid/
formaldehyde
Hydroxy, methyl ester, acetic
acid
Acetic acid Ethyl acetate
2,3-Butanedione 3-Hydroxy, 2-butanone
2890 Y. Xu et al. / Applied Energy 87 (2010) 28862891
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