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Direct Hydrogenation of Acetic Acid in Bio-Oil with the Transition and Noble Metal-
Loaded Catalysts

Article in Journal of Bioprocess Engineering and Biorefinery · December 2013

DOI: 10.1166/jbeb.2013.1067

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 ARTICLE
Journal of Bioprocess
Copyright © 2014 American Scientific Publishers Engineering and Biorefinery
All rights reserved Vol. 2, 1–4, 2014
Printed in the United States of America www.aspbs.com/jbeb

Direct Hydrogenation of Acetic Acid in Bio-Oil with the

Transition and Noble Metal-Loaded Catalysts
Jimin Zeng1 , Ming Zhao2 , Junyu Liang2 , Xing Chen1 , Huiyan Zhang1 ,
Dekui Shen1 , Shanshan Shao1 , and Rui Xiao1
∗
1
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, P. R. China
2
Electric Power Research Institute, Yunnan Electric Power Test and Research Institute (Group), Kunming 650217, P. R. China

Activated carbon supported the transition metal Ni, Mo and the noble metal Pd catalysts were evaluated for direct hydro-
genation of acetic acid in bio-oil for 10 hours at initial hydrogen pressure of 5 MPa and temperature of 190  C. Hydrogenation
of acetic acid over the catalyst of 5% Pd/C at temperature conditions of 170–200  C was simulated by using Aspen Plus,
and the comparison was made between the results of real reaction and the results calculated by Aspen Plus. The results
showed that the experiment over the catalyst of 30% Ni–5% Pd/C performed the greatest selectivity to ethanol of 76.29%.
Meanwhile, the experiment over the catalyst of 5% Pd/C showed the best conversion of acetic acid in bio-oil after 10-hour
reaction. The comparison showed that at temperature conditions of 180–200  C, the conversions of acetic acid in bio-oil
calculated by Aspen Plus were close to the real experiments.
KEYWORDS: Bio-Oil, Acetic Acid, Metal-Loaded Catalysts, Hydrogenation, Aspen Plus.

1. INTRODUCTION Examples included hydrodeoxygenation, (Şenol et al.,

Biomass is one of the most promising renewable energy
sources to replace fossil fuels, and it has a unique char-
acteristic in that it is a feedstock for the production of
chemicals as well as gaseous and liquid fuels. It is also
environment-friendly for its negligible sulfur, nitrogen, and
ash content (resulting in low emissions of harmful pollu-
tants). Comparing to fossil fuel, biofuel brings much less
harmful pollutants than it. Biomass utilization technologies
contain direct combustion technology, thermo-chemical
conversion technology, biotransformation technology and
liquefaction technology. (Huber et al., 2006; McKendry,
2002; Simonetti and Dumesic, 2009) Many researchers
are focusing on the bio-oil obtained from the fast pyrol-
ysis of biomass in thermo-chemical conversion technol-
ogy. However, the chemical composition of bio-oil is
extremely complex, which contains aldehydes, ketones,
phenols, organic acids, alcohols. It makes the properties of
bio-oil with low heating value, low thermal stability, high
oxygen content (35–40 wt.%) and low pH value (pH =
2–3). (Czernik and Bridgwater, 2004) Therefore, it must
be upgraded if used as substitutes for diesel and gasoline
fuels.
Various technologies were under development for con-
verting bio-oil to chemicals and transportation fuels.
∗
Author to whom correspondence should be addressed.
Emails: ruixiao@seu.edu.cn, 101011398@seu.edu.cn
2005) emulsification, steam reforming and catalytic crack-
ing, (Vispute et al., 2010) which in order to reduce the
oxygen content and make it more stable. Many researchers
concentrated on hydrogenation of bio-oil to liquid fuels
and chemicals using metal-loaded catalysts. (Fuente et al.,
2001) Metals like Ru, Pt, Pd, Ni, Mo, Co and Cu were
very popular to be made in the catalysts. (Luque and Clark,
2010; Olcay et al., 2010; Zhang et al., 2007) Nevertheless,
some of the results were not quite well. The reason was
that bio-oil obtained from the pyrolysis of biomass usu-
ally contained over 15% volume concentration of acetic
acid. Acetic acid is considered to be one of the most dif-
ficult compounds to be hydrogenated in bio-oil. In some
previous papers, it was mentioned to upgrade bio-oil by
esterifying. (Zhang et al., 2006) Esterification upgraded
many properties of bio-oil, but the upgraded bio-oil con-
tained a lot of esters and is not suitable to be used as
liquid fuel. There was another upgrading method, named
one-step hydrogenation-esterification (OHE). (Tang et al.,
2008; Yu et al., 2011a; b) The OHE method is one of novel
ways for upgrading bio-oil, it combined with hydrogena-
tion and esterification, but it has one problem, which is
more esterified than hydrogenated for acetic acid in bio-oil.
Direct hydrogenation of acetic acid is a promising way
to upgrade raw bio-oil. It could not only improve some
properties but also let it more suitable to be used as liquid
fuel. But it is really difficult for its low conversion rate

J. Bioprocess Eng. Biorefinery 2014, Vol. 2, No. 4 2168-5134/2014/2/001/004 doi:10.1166/jbeb.2014.1067 1

Direct Hydrogenation of Acetic Acid in Bio-Oil with the Transition and Noble Metal-Loaded Catalysts
now. This study is an attempt to investigate direct hydro-
genation of acetic acid in bio-oil and build up a mathemati-
cal model by using Aspen Plus. The metal-loaded catalysts
combining with transition and noble metals have been little
investigated in hydrogenation of bio-oil, previously. Aspen
Plus is widely used to simulate the equilibrium of chemi-
cal reactions, but it is novel to use the Arrhenius Equation
fitting with the hydrogenation and simulating its chemi-
cal kinetics by the software, mathematically. Moreover, the
comparison between simulation and real reactions is really
promising.
2. MATERIALS AND METHODS
2.1. Materials and Catalysts Preparation
The catalyst of 5% Pd/C was purchased from
Aladdin Company, China. Ni(NO3 )2 · 6H2 O was pur-
chased from Chengdu Kelong Chemical Reagent Factory
and (NH4
6 Mo7 O24 · 4H2 O was purchased from Tianjin
Guangfu Science and Technology Development Co., Ltd.
One of the catalysts used in these experiments was transi-
tion and noble metal-loaded of 30% Ni–5% Pd/C, which is
prepared by impregnating process as follows: noble metal-
loaded catalyst of 5% Pd/C and 30 wt.% Ni of Ni(NO)3 ·
6H2 O were in a certain volume of de-ionized water to
be impregnated for 36 hours (typically 15 mL de-ionized
water and 1.486 g Ni(NO)3 · 6H2 O per gram of 5% Pd/C)
and dried at 105  C for 5 h. Then, they were calcined in
N2 atmosphere at 400  C for 4 h and reduced in H2 atmo-
sphere at 400  C for 4 h to reduce Ni2+ to Ni0 . The same
way for the catalyst of 30% Mo-5% Pd/C prepared except
used (NH4 )6 Mo7 O24 · 4H2 O to replace Ni(NO3 )2 · 6H2 O.
2.2. Catalytic Activity Evaluation
The chemical compositions in bio-oil are extremely com-
plex, and the authors focus on hydrogenation of acetic
acid, which is one of the main compositions in bio-oil.
The acetic acid was purchased from Shanghai Jiuyi Chem-
ical Reagent Co., Ltd. and the reactant was a volume con-
centration of 20% acetic acid solution (100 mL). A total
of 0.3 g catalyst was used in the catalytic reaction. The
hydrogenation experiments were conducted in a 200 mL
autoclave. The autoclave was flushed three times with
hydrogen to remove oxygen from the setup. The working
conditions were shown as follows: temperature of 190  C,
initial H2 pressure of 5 MPa and stirring speed of 400 rpm.
After a 10-hour reaction, the hydrogen was released and
the reactor content was cooled down to room temperature.
The products were qualified by GC−FID/TCD (Shimadzu
2014 GC, Japan).
2.3. Hydrogenation Over 5% Pd/C in Simulation
The Arrhenius Equation was used to hand out Activation
Energy Ea and pre-exponential factor A. The hydrogena-
tion of acetic acid over the 5% Pd/C was simulated by
using Aspen Plus at four different temperature conditions:
2 J. Bioprocess Eng. Biorefinery 2: 1–4, 2014
Zeng et al.
170  C, 180  C, 190  C and 200  C. The results were
compared with the real reactions.
3. RESULTS AND DISCUSSION
3.1. Activity and Selectivity of Hydrogenation Over
Catalysts in the Experiment
The conversion of acetic acid, the final yield of ethanol and
the selectivity after 10 h were showed in Table I, respec-
tively. 5% Pd/C exhibited the best conversion and 30%
Ni–5% Pd/C performed the greatest selectivity to ethanol
over the three different kinds of catalysts. In order to clar-
ify the relation of conversion and selectivity with time,
Figures 1 and 2 were carried out.
Although 5% Pd/C presented the greatest activity after
the whole reaction, 30% Ni–5% Pd/C performed more sta-
ble than 5% Pd/C. It could be confirmed that 30% Ni–5%
Pd/C reached over 8% just after 4 hours. The three dif-
ferent kinds of catalysts were all showed that the hydro-
genation of acetic acid increased with time on the stream
(Fig. 1.). Concerning the transition metal Ni had some syn-
ergistic effect with Pd, Rabo et al. pointed out Ni reacted
with H2 at 200  C–300  C, which makes the hydrogenat-
ing process becoming faster. (Rabo et al., 1978; Yoshida
et al., 1984) The conversion over 5% Pd/C being greatest
was probably because esterification to ethyl acetate was
activated in the last two hours. (Neri et al., 2001; Xia et al.,
2005)
Table I. Activity and selectivity after 10-hour hydrogenation over
catalysts.
Catalysts 5% Pd/C 30% Ni–5% Pd/C 30% Mo–5% Pd/C
Conversion (vol %) 961 814 776
Final yield (vol %)
Ethanol 430 621 271
Byproducts 531 193 505
Selectivity∗ (%)
Ethanol 4475 7629 3492
∗
Note: selectivity (A) = Final yield (A)/Conversion (Total) × 100%.
Fig. 1. The conversion of acetic acid with time over the catalysts.
Zeng et al. Direct Hydrogenation of Acetic Acid in Bio-Oil with the Transition and Noble Metal-Loaded Catalysts

Fig. 3. The model of hydrogenation in Aspen Plus.

Fig. 2. Selectivity to ethanol with time over the catalysts.

Hydrogenation over 30% Ni–5% Pd/C performed the

greatest selectivity to ethanol. Besides, it was not good
over 30% Mo–5% Pd/C (Fig. 2.). The reason was probably
that Ni made esterification more difficult, while Mo made
it easier and most of ethanol became ethyl acetate with
acetic acid.

3.2. Hydrogenation of Acetic Acid in Bio-Oil Over

5% Pd/C by Using Aspen Plus Fig. 4. Hydrogenation at different temperature conditions over 5% Pd/C
in simulation.
Hydrogenation at different temperature conditions have
been studied in our work. The Arrhenius Equation was
built by the datum showed in Tables II and III. 152139.3 J/mol and 3783 × 1011 , respectively. The result
The datum of ln k and 1/T in Table III were used to get showed that the hydrogenation of acetic acid was really
Activation Energy Ea and pre-exponential factor A in the difficult although 5% Pd/C was used as the catalyst.
Arrhenius Equation (2). (Laidler, 1984)

 The simulation of the hydrogenation over 5% Pd/C was
Ea studied by using Aspen Plus (Fig. 3.). Activation Energy
k = A · exp − (1)
R·T Ea of 152139.3 J/mol, pre-exponential factor A of 3783 ×
E 1011 and the hydrogen pressure of 5 MPa were input in the
ln k = ln A − a (2) software. After the simulation, the result of hydrogenation
R·T
at different temperature conditions was showed in Figure 4
After a simple mathematical calculation, Activa-
and Table V.
tion Energy Ea and pre-exponential factor A were
The conversion of acetic acid increased when tempera-
ture growing from 170  C to 200  C (Fig. 4.). The con-
Table II. Hydrogenation at different temperature conditions over 5% version of simulation was really close to the real reaction
Pd/C. at 190  C, whose error was just − 7.3%, and the errors
Conversion (%) T (K) k (×10−6 mol/s) Ln k 1/T (×10−3 ) at 180  C and 200  C were 17.4% and − 21.8%, respec-
tively. However, at 170  C, the error was so huge and not
1.56 443.15 0.433 −14652 2.257
accurate at all (Table IV). Concerning Aspen Plus itself,
6.32 453.15 1.756 −13253 2.207
9.61 463.15 2.669 −12834 2.159
13.60 473.15 3.778 −12486 2.113
Table IV. Comparison between simulation and the real reaction.

Temperature ( C) 170 180 190 200

Table III. The datum to build up the Arrhenius Equation. Temperature (K) 44315 45315 46315 47315
AVO T1 + T2
∗ Ln k 1/T (×10−3 ) RCa (vol %) 156 632 961 1360
SCb (vol %) 622 742 891 1064
(443.15 K + 46315 K) −13743 2.208 Errorc (%) 298 174 −73 −218
(453.15 K + 47315 K) −12870 2.160
Notes: a RC = Real conversion of acetic acid; b SC = Simulating conversion of acetic
Note: ∗ AVO (T1 + T2 ) = (data of T1 + data of T2
/2. acid; c Error = (Simulating conversion-Real conversion)/Real conversion ×100%.

J. Bioprocess Eng. Biorefinery 2: 1–4, 2014 3

 Direct Hydrogenation of Acetic Acid in Bio-Oil with the Transition and Noble Metal-Loaded Catalysts
it was widely used to simulate the equilibrium of chemi-
cal reactions. (Wooley and Putsche, 1996) And the reason
was probably that hydrogenation was not in equilibrium
at 170  C just after 10 hours. It could also be confirmed
that the mathematical model of the Arrhenius Equation fit-
ted in with hydrogenation of acetic acid in some actual
conditions.
4. CONCLUSIONS
Direct hydrogenation of acetic acid over 5% Pd/C, 30%
Ni–5% Pd/C and 30% Mo–5% Pd/C has been investigated
in this study. 30% Ni–5% Pd/C shows great activity and
selectivity for hydrogenation. This result is properly due to
the effect of metal Ni helping produce ethanol. Aspen Plus
has been used to simulate chemical kinetics of hydrogena-
tion at different temperature conditions. The result shows
that hydrogenation at some conditions is close to the real
reaction, especially at 190  C, while it has a huge error
at 170  C. The possible reason is that hydrogenation has
not been in equilibrium in the real reaction. Direct hydro-
genation of acids in bio-oil is promising, not only because
of the acids’ corrosion to reactors, but also because of the
low heating value of the raw bio-oil. This study consol-
idates the understanding of hydrogenation of acetic acid
in bio-oil and will promote the kinetic understanding on
catalytic hydrogenation.
Acknowledgment: The authors are grateful for the
financial support from the National Hi-tech Research
and Development Program of China (863 Program)
(2012AA051801).
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