energies

Article
Liquid-Phase Hydrogenation of Maleic Acid over
Pd/Al2O3 Catalysts Prepared via
Deposition–Precipitation Method
Mi Yeon Byun 1,2 , Ji Sun Kim 3 , Jae Ho Baek 1 , Dae-Won Park 2 and Man Sig Lee 1, *
1 Ulsan Regional Division, Korea Institute of Industrial Technology (KITECH), Ulsan 44413, Korea;
miyeon1067@kitech.re.kr (M.Y.B.); jhbaek@kitech.re.kr (J.H.B.)
2 Department of Polymer Science and Chemical Engineering, Pusan National University, Busan 46241, Korea;
dwpark@pusan.ac.kr
3 Department of Chemical & Biological Engineering, The University of British Columbia, Vancouver,
BC V6T 1Z4, Canada; kjs10041012@gmail.com
* Correspondence: lms5440@kitech.re.kr; Tel.: +82-52-980-6630; Fax: +82-52-980-6639




Received: 14 November 2018; Accepted: 16 January 2019; Published: 17 January 2019


Abstract: Succinic acid (SA) is a valuable raw material obtained by hydrogenation of maleic acid (MA).
The product selectivity of this reaction is highly dependent on the reaction conditions. This study
therefore investigated the effect of the reaction temperature, hydrogen pressure, and reaction time
on the liquid-phase hydrogenation of MA by a Pd/Al2 O3 catalyst. Complete conversion of MA and
100% selectivity for SA were achieved at a temperature of 90 ◦ C, H2 pressure of 5 bar, and reaction
time of 90 min. Fumaric acid (FA) was formed as an intermediate material by hydrogenation of MA
under nonoptimal conditions. The impact of the percentage of Pd dispersion and phase of the Al2 O3
support (γ, θ + α, and α) was also examined. The Pd/Al2 O3 catalyst with 29.8% dispersion of Pd
and γ phase of Al2 O3 exhibited the best catalytic performance. Thus, catalytic activity depends not
only on the amount of Pd dispersion but also on the physicochemical properties of Al2 O3 .

Keywords: hydrogenation; succinic acid; supported catalyst; Pd catalyst

1. Introduction
The growth of the petrochemical industry has brought about environmental problems such as
industrial waste, pollution, and global warming. Therefore, many researchers have been investigating
sustainable and renewable resources. In this regard, succinic acid (SA) has attracted attention as an
eco-friendly raw material for the production of biodegradable plastics and biosolvents. SA is widely
used as an intermediate material in the production of high value products such as γ-butyrolactone,
1,4-butanediol, and tetrahydrofuran [1,2]. It is usually obtained by hydrogenation of maleic anhydride
(MAN), although the product of this reaction varies depending on the reaction conditions. Several
researches have investigated various catalysts for this reaction, such as Ru/C, Ni/HY–Al2 O3 , Pd/C,
Pd/SiO2 , Ni/TiO2 and Pd/Al2 O3 [3–9]. The reaction pathways of hydrogenation of maleic acid (MA)
are shown in Figure 1. Kim et al. reported a yield of 99.97% SA using Pd/C as the catalyst and
conducting the reaction under 1.0 MPa of H2 at 90 ◦ C for 150 min [3]. Torres et al. reported achieving
100% selectivity for succinic anhydride through the reaction catalyzed by a mesoporous Ni/TiO2
catalyst at low temperature [8]. Yuan et al. reported achieving MA conversion of 98% and succinic
anhydride selectivity of 99% using Pd/Al2 O3 catalyst under 1.0 MPa of H2 pressure and 1,4-dioxane
as solvent [5]. Among the various catalysts, the Pd/Al2 O3 catalyst has an advantage for the chemical
industry due to the high thermal stability and high dispersion of Pd [10,11]. However, few studies have
been performed on the optimization of reaction conditions for the hydrogenation of maleic acid (MA)

Energies 2019, 12, 284; doi:10.3390/en12020284 www.mdpi.com/journal/energies

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Energies 2019, 12, 284 2 of 8

on the optimization of reaction conditions for the hydrogenation of maleic acid (MA) to SA over a
to SA over a Pd/Al O3 catalyst. In our previous study, we reported that the particle size distribution
Pd/Al2O3 catalyst. In2 our previous study, we reported that the particle size distribution of Pd is
of Pd is influenced
influenced by the physicochemical
by the physicochemical properties
properties of of Al2surface
Al2O3 (specific O3 (specific surface
area and areafunctional
surface and surface
functional
groups) andgroups) and catalystconditions
catalyst preparation preparation
(pH,conditions (pH, solution
solution temperature, andtemperature, and [12,13].
reduction agent) reduction
agent) [12,13]. Herein, we investigated the effect of reaction temperature (T),
Herein, we investigated the effect of reaction temperature (T), H2 pressure (PH2), and reaction H 2 pressure (PH2 ),
time (t)
and reaction time (t) on the liquid-phase hydrogenation of MA over a Pd/Al O
on the liquid-phase hydrogenation of MA over a Pd/Al2O3 catalyst. The catalytic2 activities 3 catalyst. The catalytic
of Pd/Al2O3
activities
with varyingof percentage
Pd/Al2 O3 of with varying percentage
Pd dispersion of Pd (γ,
and Al2O3 phase dispersion
θ + α, andand Al2 O
α) were 3 phase
also (γ, θ +Finally,
compared. α, and α)
were
the also compared.
reusability Finally,
of the Pd/Al the reusability
2O3 catalyst of the Pd/Al2 O3 catalyst was assessed.
was assessed.

Figure 1. Reaction pathways in hydrogenation of maleic acid in water.

Figure 1. Reaction pathways in hydrogenation of maleic acid in water.
2. Experiment
2. Experiment
2.1. Catalyst Preparation
2.1. Catalyst Preparation
The catalyst support, Al2 O3 (≥99%, Alfa Aesar, γ phase, average particle size: 20 nm), was dried
at 105 ◦ for 4 h and calcined at various temperatures (900, 1100, and 1150 ◦ C) for 4 h. The Pd/Al O
TheCcatalyst support, Al2O3 (≥99%, Alfa Aesar, γ phase, average particle size: 20 nm), was dried at2 3
catalysts, containing
105 °C for 4 h and calcined5 wt %atPd, were prepared
various by the
temperatures deposition–precipitation
(900, 1100, and 1150 °C) for method.
4 h. The The
Pd/Aldetailed
2O3

procedure
catalysts, has been5described
containing wt% Pd, were in our previous
prepared byresearch [12]. Briefly, Al2 O3 was
the deposition–precipitation dispersed
method. in the Pd
The detailed
precursor has
procedure solution
been at 60 ◦ C, and
described the pH
in our was adjusted
previous research using 0.25 M Al
[12]. Briefly, NaOH solution.
2O3 was Reduction
dispersed in the Pdof the
precursor solution
catalyst was at out
carried 60 °C, andliquid
in the the pH was using
phase adjusted using solution
formalin 0.25M NaOH (10 wtsolution.
%, SigmaReduction
Aldrich, of
St.the
Louis,
catalyst was The
MO, USA). carried out inPd/Al
prepared the liquid phase using
2 O3 catalysts formalinas
are denoted solution
Pd/Al2(10O3 wt%, Sigma
(X)_pHY, Aldrich).
where Theheat
X is the
prepared
treatmentPd/Al 2O3 catalysts
temperature of theare
Al2denoted
O3 support,as Pd/Al
and Y2Ois3 the
(X)_pHY,
pH. Thewhere X is the heat
physicochemical treatment
properties of the
temperature of the Al O support,
catalysts are summarized in Table 1.
2 3 and Y is the pH. The physicochemical properties of the catalysts are
summarized in Table 1.

Table 1. Summary of physicochemical properties of Pd/Al2O3 catalysts [12,13].

Energies 2019, 12, 284 3 of 8

Table 1. Summary of physicochemical properties of Pd/Al2 O3 catalysts [12,13].

Pd/Al2 O3 Pd/Al2 O3 Pd/Al2 O3 Pd/Al2 O3 Pd/Al2 O3

Catalysts
(105)_pH 7.5 (900)_pH 7.5 (900)_pH 11.5 (1100)_pH 7.5 (1150)_pH 7.5
Al2 O3 phase 1 γ γ γ θ+α α
Al2 O3 surface area 2 195 146 146 54 6
Al2 O3 Pore volume 2 0.82 0.62 0.62 0.28 0.007
Al2 O3 Acidity (mmol/g) 3 0.47 0.37 0.37 0.22 0.07
Pd dispersion (%) 4 20.6 29.8 13.1 11.0 2.9
1 X-ray diffraction, 2 Brunauer–Emmett–Teller analysis of N adsorption–desorption, 3 NH3 temperature
2
programmed desorption, 4 CO chemisorption.

2.2. Hydrogenation of Maleic Acid

Liquid-phase hydrogenation of maleic acid was conducted in a 100 mL stainless steel autoclave.
MA (0.29 mol), 46 g distilled water, and 0.1 g Pd/Al2 O3 were placed in the autoclave. The reactor
was purged with nitrogen three times to remove air, and hydrogen was then used to purge out
nitrogen. The sealed autoclave was pressurized to the desired pressure and heated to the desired
temperature, and the reaction mixture was stirred at 700 rpm. The catalytic reaction was carried out for
15–90 min. The reaction products were analyzed by high-performance liquid chromatography (HPLC,
Shimadzu Co. Model Prominence) equipped with a refractive index detector and Agilent Hi-Plex
H (7.7 mm × 300 mm × 8 µm). The mobile phase was 5 mM H2 SO4 with a flow rate of 6 mL min−1 .
The MA, SA, fumaric acid (FA), and malic acid (MLA) standards (Sigma Aldrich) were analytical
grade and used without purification. The reaction was conducted at varying temperature, hydrogen
pressure, and reaction time. Conversion and selectivity were calculated as follows:

Initial mole o f MA − f inal mole o f MA

Conversion (%) = × 100 (1)
Initial mole o f MA

mole o f desired product

Selectivity (%) = × 100 (2)
Initial mole o f MA − f inal mole o f MA

3. Results and Discussion

3.1. Effect of Reaction Temperature

The effect of reaction temperature on MA hydrogenation over the Pd/Al2 O3 (900)_pH7.5
catalyst was investigated within the range of 30–110 ◦ C (Figure 2). As the reaction temperature
increased, the conversion of MA increased, while the selectivity for SA decreased from 100% to 85%.
At temperatures above 90 ◦ C, the selectivity for FA and MLA slightly increased. It has been reported
that, at high temperature, MA is unstable and can isomerize to the more stable FA [14]. On the other
hand, the isomer FA undergoes hydration to form MLA at high temperature. Thus, 90 ◦ C is the optimal
temperature for high conversion of MA and selectivity for SA.
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Figure 2. Effect of reaction temperature on maleic acid (MA) hydrogenation over Pd/Al2O3
(900)_pH7.5 at PofH2of
Figure 2. Effect
Figure 2. Effect = reaction
3 bartemperature
reaction andtemperature
t = 60 min.
on maleic acid (MA) hydrogenation over Pd/Al2 O3 (900)_pH7.5
on maleic acid (MA) hydrogenation over Pd/Al2O3
at P H2 = 3 bar and t = 60 min.
(900)_pH7.5 at PH2 = 3 bar and t = 60 min.
3.2. Effect of H2 Pressure
3.2. Effect of H2 Pressure
3.2. Effect of H2 Pressure
TheTheeffect
effectofofHH2 2pressure
pressureon on MA
MA hydrogenation
hydrogenation over the the Pd/Al
Pd/Al22O O33 (900)_pH7.5
(900)_pH7.5 catalyst
catalyst was
investigated
The effect of H2 pressure on MA hydrogenation over the Pd/Al2O3 (900)_pH7.5 catalystfrom
investigated within
within the
therange
range of
of1–15
1–15 bar
bar (Figure
(Figure 3).
3).MA
MA conversion
conversion and
and SA
SA selectivity
selectivity increased
increased was
30%30% to 100%
to 100% andand 53%53% to 100%,
to 100%, respectively,
respectively, as
asthe
the HH2 pressure
pressure increased
increased from
investigated within the range of 1–15 bar (Figure 3). MA conversion and SA selectivity increased from
2 from 11 to
to 15
15 bar.
bar. Within the
range
range
30% ofof
to 1–5
100% bar,
1–5 bar,the
and the
53%selectivity
to 100%,for
selectivity forFAFAgradually
gradually
respectively, decreased
decreased
as the from
from40%
H2 pressure 40%toto1.6%.
increased1.6%.
fromAs
As1demonstrated
demonstrated
to 15 bar. Within above,
above,
the
FAFAcan be produced by isomerization of MA at high temperature. However, FA is predominantly
rangecan be produced
of 1–5 by isomerization
bar, the selectivity of MA atdecreased
for FA gradually high temperature.
from 40% to However,
1.6%. AsFA is predominantly
demonstrated above,
produced
FAproduced
can be at produced
lowlow
at H2 pressure,
H2 by indicating
pressure, that
indicating
isomerization of MAFA
thatis an
atFA intermediate
is an
high in the
intermediate
temperature. conversion FAofisMA
in the conversion
However, toofSA.
MA Kim
predominantly to
etproduced
al. reported
SA. Kim at thatH
et low
al. the
reportedformation
that of
the FA is
formationdetermined
of FA isby the relative
determined reaction
by the rates
relative
2 pressure, indicating that FA is an intermediate in the conversion of MA to SA. Kim
of hydrogenation
reaction rates of
and protonation
ethydrogenation
al. reported that [3].
andProtonation
protonation
the formation occurs
[3].
of FA faster than hydrogenation
Protonation
is determined occursby faster at Hhydrogenation
than
the relative 2 pressures lower
reaction rates of atthan 5 bar but
H2 pressures
hydrogenation
slower
lower
and atthan
higher
5 bar
protonation pressures.
butProtonation
[3]. slower at higher
occurspressures.
faster than hydrogenation at H2 pressures lower than 5 bar but
slower at higher pressures.

Figure 3. Effect of H pressure on MA hydrogenation over Pd/Al O (900)_pH7.5 at T = 90 ◦ C and

Figure 3. Effect of H22 pressure on MA hydrogenation over Pd/Al
2 3
2O3 (900)_pH7.5 at T = 90°C
t = 60 min.
and t = 60 min.
Figure 3. Effect of H2 pressure on MA hydrogenation over Pd/Al2O3 (900)_pH7.5 at T = 90°C
and t = 60 min.
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2019, x FOR
284 PEER REVIEW 5 of 8 8
5 of

3.3.
3.3.Effect of of
Effect Reaction Time
Reaction Time
Theeffect
The effectofofreaction
reactiontimetime on
on MA
MA hydrogenation
hydrogenation over over the
thePd/Al
Pd/Al22OO33 (900)_pH7.5
(900)_pH7.5 catalyst
catalyst was
was
investigated within the range of 15–90 min at a fixed reaction temperature of 90 ◦ C and H pressure of
investigated within the range of 15–90 min at a fixed reaction temperature of 90 °C and H22 pressure of
5 5bar
bar(Figure
(Figure4).4).The
Theconversion
conversionofofMA MAdramatically
dramaticallyincreased
increasedup up to
to 80%
80% upon
upon increasing
increasing the
the reaction
reaction
time from 15 to 30 min. It subsequently changed more gradually as the reaction time was prolonged
time from 15 to 30 min. It subsequently changed more gradually as the reaction time was prolonged
from3030toto9090min.
from min.TheTheselectivity
selectivityforforFA
FAinitially
initiallyincreased
increased between
between 15 15 and
and 30
30 min
min and
and then
then decreased
decreased
as the reaction time increased from 30 to 90 min. Thus, 100% MA conversion and SA selectivity were
as the reaction time increased from 30 to 90 min. Thus, 100% MA conversion and SA selectivity were
achievedatata atemperature
temperatureofof9090°C, ◦ C, H pressure of 5 bar, and reaction time of 90 min.
achieved 2
H2 pressure of 5 bar, and reaction time of 90 min.

Figure 4. Effect of reaction time on MA hydrogenation over Pd/Al2 O3 (900)_pH7.5 at T = 90 ◦ C and

Figure 4. Effect of reaction time on MA hydrogenation over Pd/Al2O3 (900)_pH7.5 at T = 90°C
PH2 = 5 bar.
and PH2 = 5 bar.
3.4. Effect of Al2 O3 Support Properties and Pd Dispersion
3.4. Effect of Al2O3 Support Properties and Pd Dispersion
The effect of the properties of the Al2 O3 support and dispersion of Pd on the catalytic activity
for liquid-phase hydrogenation of MA were investigated under the following conditions: T = 90 ◦ C,
The effect of the properties of the Al2O3 support and dispersion of Pd on the catalytic activity for
PH2 = 5 bar, t = 60 min, and stirring rate = 700 rpm. The physicochemical properties of the different
liquid-phase hydrogenation of MA were investigated under the following conditions: T = 90 °C, PH2 = 5
Pd/Al2 O3 catalysts are summarized in Table 1. The order of decreasing catalytic activity was Pd/Al2 O3
bar, t = 60 min, and stirring rate = 700 rpm. The physicochemical properties of the different Pd/Al2O3
(900)_pH7.5 > Pd/Al2 O3 (105)_pH7.5 > Pd/Al2 O3 (900)_pH11.5 > Pd/Al2 O3 (1100)_pH7.5 > Pd/Al2 O3
catalysts are summarized in Table 1. The order of decreasing catalytic activity was Pd/Al2O3
(1150)_pH7.5 (Figure 5). The conversion of MA and selectivity for SA increased with increasing
(900)_pH7.5 > Pd/Al2O3 (105)_pH7.5 > Pd/Al2O3 (900)_pH11.5 > Pd/Al2O3 (1100)_pH7.5 > Pd/Al2O3
dispersion (i.e., decreasing particle size) of Pd, indicating that Pd was the more active species in the
(1150)_pH7.5 (Figure 5). The conversion of MA and selectivity for SA increased with increasing
hydrogenation of MA. The dispersion of Pd in the Pd/Al2 O3 (900)_pH11.5 and Pd/Al2 O3 (1100)_pH7.5
dispersion (i.e., decreasing particle size) of Pd, indicating that Pd was the more active species in the
catalysts was similar at 13.1% and 11.0%, respectively. However, the catalysts exhibited significantly
hydrogenation of MA. The dispersion of Pd in the Pd/Al2O3 (900)_pH11.5 and Pd/Al2O3 (1100)_pH7.5
different MA conversion and SA selectivity owing to the difference in the properties of the Al2 O3
catalysts was similar at 13.1% and 11.0%, respectively. However, the catalysts exhibited significantly
support. It has been reported that the isomerization of MA to FA can occur without a catalyst and
different MA conversion and SA selectivity owing to the difference in the properties of the Al2O3
is strongly affected by the concentration of maleic acid, the reaction temperature, and the pH of the
support. It has been reported that the isomerization of MA to FA can occur without a catalyst and is
solution [15]. Al2 O3 in the Pd/Al2 O3 (900)_pH11.5 catalyst was in the γ phase, which has a large
strongly affected by the concentration of maleic acid, the reaction temperature, and the pH of the
specific surface area and strong acid sites, whereas in the Pd/Al2 O3 (1100)_pH7.5 catalyst, it was in
solution [15]. Al2O3 in the Pd/Al2O3 (900)_pH11.5 catalyst was in the γ phase, which has a large specific
the θ + α phase, which has a small specific surface area and weak acid sites. The physicochemical
surface area and strong acid sites, whereas in the Pd/Al2O3 (1100)_pH7.5 catalyst, it was in the θ + α
properties of the Al2 O3 support affect the adsorption strength of the reactant and Pd nanoparticles on
phase, which has a small specific surface area and weak acid sites. The physicochemical properties of
the active sites. Al2 O3 in the γ phase can provide a large number of active sites for the hydrogenation
the Al2O3 support affect the adsorption strength of the reactant and Pd nanoparticles on the active sites.
reaction and allows increased retention time on the catalyst surface, resulting in high conversion of MA
Al2O3 in the γ phase can provide a large number of active sites for the hydrogenation reaction and
and high selectivity for SA. In contrast, the low Pd dispersion, small specific surface area, and weak
allows increased retention time on the catalyst surface, resulting in high conversion of MA and high
acid sites in Pd/Al O3 catalysts with Al2 O3 in the θ + α or α phase can cause reduced retention time
selectivity for SA. In 2contrast, the low Pd dispersion, small specific surface area, and weak acid sites in
Energies 2018, 11, x FOR PEER REVIEW 6 of 8
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Energies 2019, 12, 284 6 of 8
Pd/Al2O3 catalysts with Al2O3 in the θ + α or α phase can cause reduced retention time on the catalyst
Pd/Al2Oresulting
surface, 3 catalysts
inwith Al2O3 in the
low efficiency forθthe + αhydrogenation
or α phase canreaction.
cause reduced retention
These results timethat
suggest on the catalyst
a decrease
in on
thethe
surface, catalyst
resulting
retention surface,
in low
time of MAresulting
and Hin
efficiency low
2 for
on the
theefficiency
catalyst for
hydrogenation the hydrogenation
surface reaction.
leads to These reaction.
a lowerresults These
rate.results
suggest
reaction suggest
that a decrease
inthat
thearetention
decrease time
in theofretention
MA andtime H2 on of the
MAcatalyst
and H2 surface
on the catalyst
leads tosurface
a lowerleads to a lower
reaction rate. reaction rate.

Figure 5. Effect of Al2O3 phase and Pd dispersion on MA hydrogenation at T =◦ 90°C, PH2 = 5

Figure 5. Effect of Al2 O3 phase and Pd dispersion on MA hydrogenation at T = 90 C, PH2 = 5 bar,
Figure
bar, and5.t =Effect of Al2O3 phase and Pd dispersion on MA hydrogenation at T = 90°C, PH2 = 5
60 min.
and t = 60 min.
bar, and t = 60 min.
3.5. Reusability
3.5. Reusability of of
Pd/Al 2O3O
Pd/Al 2 (900)_pH
3 (900)_pH7.57.5
Catalyst in in
Catalyst Hydrogenation
Hydrogenation of MA
of MA
3.5. Reusability of Pd/Al2O3 (900)_pH 7.5 Catalyst in Hydrogenation of MA
Reusabilityand
Reusability andstability
stabilityare
areimportant
importantfactors
factorsininthe
the chemical
chemical industry.
industry. The
The reusability
reusability of
of the
the
Pd/Al2O2
O
Pd/AlReusability
3 (900)_pH7.5
3 (900)_pH7.5
catalyst
and stability
catalyst are was therefore
wasimportant investigated.
therefore factors Liquid-phase
in the Liquid-phase
investigated. chemical industry. hydrogenation of MAofwas
of
The reusability
hydrogenation MA the
was
carried
Pd/Al O out under
(900)_pH7.5 optimized
catalystreaction
was conditions.
therefore After each
investigated. reaction,
Liquid-phase the catalyst was
hydrogenation
carried out under optimized reaction conditions. After each reaction, the catalyst was separated from
2 3
separated
of MA from
was
thereactant
the reactant
carried andwashed
out under
and washed
optimized with
with deionized
reaction
deionized water.The
conditions.
water. The conversion
After of MA
each reaction,
conversion of MA and
the selectivity
catalyst
and for SA
SA did
was separated
selectivity for not
didfrom
not
decrease
the reactant
decrease significantly
and washed
significantly for seven
for with cycles,
sevendeionized indicating
water. The
cycles, indicating that the Pd/Al
conversion
that the Pd/Alof O
22OMA
(900)_pH7.5 catalyst
and selectivity
33 (900)_pH7.5
was
for was
catalyst stable
SA did not
stable
during
decrease
during the liquid-phase
thesignificantly
liquid-phasefor hydrogenation of MA
seven cycles,ofindicating
hydrogenation (Figure
MA (Figure that 6).
6).the Pd/Al2O3 (900)_pH7.5 catalyst was stable
during the liquid-phase hydrogenation of MA (Figure 6).

Figure 6. Reusability of Pd/Al2 O3 (900)_pH7.5 catalyst in MA hydrogenation at T = 90 ◦ C, PH2 = 5 bar,

Figure
and t =6.90
Reusability
min. of Pd/Al2O3 (900)_pH7.5 catalyst in MA hydrogenation at T = 90°C, PH2
= 5 bar, and t = 90 min.of Pd/Al2O3 (900)_pH7.5 catalyst in MA hydrogenation at T = 90°C, PH2
Figure 6. Reusability
4. Conclusions
= 5 bar, and t = 90 min.
Liquid-phase hydrogenation of MA to SA with different Pd/Al2 O3 catalysts was investigated,
focusing mainly on the effect of two factors on catalytic activity and selectivity: reaction conditions
Energies 2019, 12, 284 7 of 8

and physicochemical properties of the catalyst. The effect of the reaction conditions was investigated
by varying the reaction temperature, H2 pressure, and reaction time. Depending on the reaction
conditions, FA was formed as an intermediate or final product through isomerization of MA. Under
the optimal reaction conditions of T = 90 ◦ C, PH2 = 5 bar, t = 90 min, 100% MA conversion and 100%
SA selectivity were achieved using the Pd/Al2 O3 (900)_pH7.5 catalyst. The effect of the Al2 O3 phase
and Pd dispersion were also investigated. Catalytic activity and selectivity were found to increase
with Pd dispersion. The characteristics of the Al2 O3 phase strongly affected the adsorption strength of
the reactant and Pd nanoparticles on the active sites and, consequently, the catalytic activity.

Author Contributions: Investigation and writing original draft preparation, M.Y.B.; Investigation, J.S.K.; Formal
analysis, J.H.B.; writing—review and editing, D.-W.P. and M.S.L.; supervision, M.S.L.
Funding: This research was financially supported by DR AXION CO. (Project No. IR180054) and the Korea
Institute of Industrial Technology (KITECH) (Project No. EE180054 and JA180001).

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