Highly active and selective nickel-platinum catalyst for the low temperature hydrogenation of maleic anhydride to succinic anhydride and synthesis of succinic acid at 40 °c

Article abstract of DOI:10.1007/s10562-010-0533-7

PtNi bimetallic and Ni monometallic catalysts supported on HY-Al ₂O₃, HX-Al₂O₃, ZSM-5-Al ₂O₃, USY-Al₂O₃, Beta-Al ₂O₃ and Al₂O₃ were prepared and evaluated for the hydrogenation of maleic anhydride in the temperature range of 40-150 °C. Results from flow reactor studies showed that supports strongly affected the catalytic properties of different bimetallic and monometallic catalysts. The results showed that the HY-Al₂O₃ support exhibited the highest activity and selectivity. Using NiPt/Al₂O ₃-HY catalyst and performing the reaction, it was possible to carry out the lowest reaction temperature ever carried at 100% conversion. Adding a small amount of Pt (0.5) to the Ni (5%)/Al₂O₃-HY catalyst that is effective for increasing the selectivity and activity. We also found that PtNi is an efficient catalyst for the one-pot conversion of maleic acid into succinic acid with 100% conversion at 40 °C. Graphical Abstract: Hydrogenation activity was found to correlate to the extent of PtNi bimetallic bond formation, as characterized by the analysis of XRD and TPR.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-010-0533-7

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Catal Lett (2011) 141:565–571
DOI 10.1007/s10562-010-0533-7
Highly Active and Selective Nickel–Platinum Catalyst for the Low
Temperature Hydrogenation of Maleic Anhydride to Succinic
Anhydride and Synthesis of Succinic Acid at 40 °C
•
Jie Li Wei-Ping Tian Li Shi
•
Received: 17 October 2010 / Accepted: 1 December 2010 / Published online: 4 January 2011
Ó Springer Science+Business Media, LLC 2010
Abstract PtNi bimetallic and Ni monometallic catalysts
supported on HY–Al2O3, HX–Al2O3, ZSM-5–Al2O3,
USY–Al2O3, Beta–Al2O3 and Al2O3 were prepared and
evaluated for the hydrogenation of maleic anhydride in the
temperature range of 40–150 °C. Results from flow reactor
studies showed that supports strongly affected the catalytic
properties of different bimetallic and monometallic cata-
lysts. The results showed that the HY–Al2O3 support
exhibited the highest activity and selectivity. Using NiPt/
Al2O3–HY catalyst and performing the reaction, it was
possible to carry out the lowest reaction temperature ever
carried at 100% conversion. Adding a small amount of Pt
(0.5) to the Ni (5%)/Al2O3–HY catalyst that is effective for
increasing the selectivity and activity. We also found that
PtNi is an efficient catalyst for the one-pot conversion of
maleic acid into succinic acid with 100% conversion at
40 °C.
c-butyrolactone (GBL), tetrahydrofurane (THF), and 1,4-
butanediol (BDO), are valuable products that find a wide
market as solvents or as starting material for polymers like
polyuretanes. In particular, SA is required as intermediate
for the chemical, pharmaceutical and food industries [1].
These compounds are produced by mainly four pro-
cesses: the Reppe process, the Arco process, the Mitsubishi
Kasei process, and the Davy McKee [4]. However, these
processes present some disadvantages. The Reppe process
uses acetylene and formaldehyde as starting material, and
severe reaction conditions (140–280 bar, 250–350 °C) [5].
The Davy McKee process needs two different reactors,
catalysts and reaction conditions [6].
Compared to the other processes, hydrogenation of
maleic anhydride is the most direct, environmentally
benign, and economic way to produce succinic anhydride.
The reactions were carried out over several types of noble
metal-based catalysts, such as Pd [7], Ru [8], Cu [9], both
in liquid phase and gas phase. The analysis of literatures on
hydrogenation of MA shows that the most papers refer to
catalytic studies at temperature over 200 °C by batch
process, while limited attention has been devoted to flow
condition at temperature under 100 °C conditions [5, 10–
12]. Moreover, many questions concerning catalyst stabil-
ity, reaction and deactivation are still open questions.
It is well known that bimetallic catalysts often show
properties that are distinctly different from those of the
corresponding monometallic catalysts. However, relatively
few articles on the hydrogenation of MA to SA, in general,
and by bimetallic catalysts, in particular, have been pub-
lished. In a recently published work by the authors [13],
hydrogenation of maleic anhydride was investigated over
Ni-loaded zeolites catalysts. The results indicated that
zeolites were excellent supports for SA production from
MA hydrogenation.
Keywords Al2O3–HY ꢀ Maleic anhydride ꢀ Pt–Ni ꢀ
Hydrogenation ꢀ Succinic anhydride
1 Introduction
The reaction network for maleic anhydride (MA) hydro-
genation is shown in Fig. 1. [1–3]. In this process, both
hydrogenation and hydrogenolysis reactions are involved.
Some of the reaction products, succinic anhydride (SA),
J. Li ꢀ W.-P. Tian ꢀ L. Shi (&)
The State Key Laboratory of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237, China
e-mail: yyshi@ecust.edu.cn
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J. Li et al.
maleic acid
O
succinic acid
2.2 Catalyst Characterization
O
HO
1,4-butanediol
-butyrolactone
HO
OH
X-ray diffraction in situ X-ray diffraction patterns during
reduction of catalysts were obtained with a Bruker D8
Advance X-Ray diffractometer equipped with an atmo-
sphere and temperature control stage and using CuKa
radiation operated at 40 kV and 100 mA. The powder
diffraction patterns were recorded in the 2h range from 10°
to 80°.
OH
O
O
maleic anhydride
succinic anhydride
tetrahydrofuran
O
O
O
O
O
O
O
O
O
Temperature-programmed reduction (TPR) of H2 was
carried out on Auto Chem 2910 (Micromeritics) instru-
ment. In a typical experiment, 0.050 g of calcined catalyst
was exposed to a reducing gas consisting of 5.0 vol.% H2
in Ar with a temperature ramp from ambient temperature to
800 °C at a heating rate of 10 °C/min.
butyric acid
n-butanol
propionic acid
n-propanol
Fig. 1 Reaction scheme of hydrogenation of maleic anhydride
2.3 Catalytic Test
The objective of the present study was to develop a
highly efficient, more stable catalyst for hydrogenation of
maleic anhydride at relatively low temperature to produce
SA with high selectivity. A series of supported Ni and NiPt
catalysts have been studied. The effects of the support (HY,
HX, ZSM-5, Beta, USY, Al2O3) and the reaction condi-
tions (temperature, pressure, WHSV) on the catalyst
activity, selectivity and stability have been investigated and
the best catalyst formulation with respect to selectivity and
activity have been identified. Moreover, the results of the
investigation of hydrogenation of MA on the selected NiPt/
HY–Al2O3 catalyst at 40 °C and the deactivation of a
reason were reported. Owning to the high activity of PtNi
for MA hydrogenation and the fact that MA is the main
precursor for the production of succinic acid, we have also
carried out the catalytic synthesis of succinic acid starting
from maleic acid at 40 °C, this help the viability and
economics of the process.
The reaction was performed in a fixed-bed reactor operated
in the down flow mode. The reaction temperature was
measured with a thermocouple in contact with the catalyst
bed. The organic feed consisted of a solution of maleic
anhydride in c-butyrolactone (22 wt%) and was fed into the
reactor by a micro-syringe pump. For each experiment, 1 g
of unreduced catalyst (20–40 mesh) was loaded into the
flow reactor. The catalyst was reduced in situ at atmo-
spheric pressure with H2 (flow rate 32 cm3/min) for 3 h.
The products were analyzed using an Agilent 6890 N gas
chromatograph (flame ionization detector, HP-5 column,
30 m 9 5 mm 9 0.25 lm) and confirmed by gas chro-
matography-mass spectroscopy (GC-MS).
Maleic anhydride (MA) conversion and selectivity to the
product i was calculated according to:
MAin ꢁ MAout
XMAð%Þ ¼
Sið%Þ ¼
ꢂ 100
ð1Þ
ð2Þ
MAin
Producti;out
2 Experimental
ꢂ 100
MAin ꢁ MAout
2.1 Catalyst Preparation
where MAin, MAout and Producti,out represent the concen-
tration of reactant or products entering (in) or leaving (out)
the reactor.
The catalysts used in this study, 5%Ni/Al2O3–HY (Al2O3/
HY mass ratio *0.4), were prepared by the kneading
method using c-Al2O3, HY zeolites, and Ni2O3 (Aldrich).
The 0.5 wt%Pt–5 wt%Ni/Al2O3–HY bimetallic catalyst
was prepared using H2PtCl6ꢀ6H2O (Aldrich, 99%) and
Ni2O3. All the catalysts were dried overnight at 120 °C in
an oven, and then calcined in air at 550 °C for 3h. The
5 wt%Ni/Al2O3–HY (HX, ZSM-5, Beta, USY and Al2O3)
and 0.5 wt%Pt–5 wt%Ni/Al2O3–HY (HX, ZSM-5, Beta,
USY and Al2O3) catalysts were also prepared using the
same method. More details can be found in a previous
study [13].
3 Results and Discussion
3.1 Catalyst Characterization
3.1.1 XRD Analysis of Optimizing Catalysts
XRD patterns of two optimizing catalysts are shown in
Fig. 2. The characteristic peaks for NiO species at
2h = 37.24°, 43.34° and 64.48° corresponding to the
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Highly Active and Selective Nickel–Platinum Catalyst
567
10%Ni-0.5%Pt/Al2O3-HY
5%Ni-0.5%Pt/Al2O3-HY
0
100
200
300
400
500
600
700
800
0
10
20
30
40
50
60
70
80
90
2θ (degrees)
Temperature
Fig. 3 Temperature-programmed reduction (TPR) profiles of the
5%Ni–0.5%Pt/Al2O3-HY catalyst
Fig. 2 X-ray diffraction pattern of calcined 5%Ni–0.5%Pt/Al2O3-HY
and 10%Ni–0.5%Pt/Al2O3-HY
3.2.1 Comparison of Different Catalyst Supports
planes (1 1 1), (2 0 0) and (2 2 0) of cubic NiO species,
respectively [14]. The XRD results also clearly show that
the concentration of NiO increased with Ni loading. Peaks
at 2h = 75.50° and 79.38° for Ni2O3 species were visible
at Ni loading of around 10 wt%. The XRD characteristic
peaks associated with Pt0 or PtO phase were not observed
in the two samples. This was probably due to the very low
amount of Pt (0.5 wt%) present and/or a very good dis-
persion of Pt phase on the supports.
The bimetallic and the corresponding monometallic catalysts
were evaluated for MA hydrogenation at 140 °C and 1MPa
pressure. As shown in Table 1, the conversion of maleic
anhydride was nearly 13% for 5%Ni/Beta–Al2O3, about 35%
for 5%Ni/USY–Al2O3, about 70% for 5%Ni/ZSM-5–Al2O3
and 5%Ni/Al2O3, and nearly 90% for 5%Ni/HX–Al2O3 and
5%Ni/HY–Al2O3. In comparison, the supported PtNi bime-
tallic catalysts showed much higher conversion. Furthermore,
the four supported PtNi bimetallic catalysts exhibited quite
different catalytic activities and selectivities. As present in
Tab.1, the conversion of maleic anhydride was about 100%
over 5%Ni–0.5%Pt/HY–Al2O3 and 5%Ni–0.5%Pt/HX–
Al2O3 catalysts, which were much higher than Beta–Al2O3,
USY–Al2O3 or ZSM-5–Al2O3 supported PtNi bimetallic
catalysts. In summary, HY–Al2O3 supported PtNi bimetallic
catalysts exhibited much better performance. And the con-
version of maleic anhydride over PtNi bimetallic catalysts
followed the trend: HY–Al2O3 * HX–Al2O3 [ USY–
Al2O3 *ZSM-5–Al2O3 [Beta–Al2O3. However, the SA
selectivity followed another trend: HY–Al2O3 [HX–
Al2O3 [ZSM-5–Al2O3 [USY–Al2O3 [Beta–Al2O3 over
the bimetallic catalysts. Additionally, all the PtNi bimetallic
catalysts showed much higher activities than the Ni mono-
metallic catalysts.
3.1.2 TPR of 5%Ni–0.5%Pt/Al2O3–HY Catalyst
In order to decide the reduction conditions, the TPR
experiment was carry out. The TPR profiles of the samples
are presented in Fig. 3. The presence of Ni3? in the catalyst
can be precluded by the absence of a reduction peak at
260 °C [9, 13]. The peak with Tmax at 300 °C can be
attributed to the reduction of NiO particles with no inter-
action with the support [15]. The interaction of NiO with
the support decreases its reducibility. The peak with Tmax at
around 450 °C thus can be assigned to the Ni2? of the NiO
species interacting with the support and are not due to the
Ni silicate/aluminate peak, because the reduction peak of
Ni silicate/aluminate would appear at a much higher tem-
perature. The peak with Tmax around 600 °C may be due to
the formation of amorphous Ni silicate/aluminate species
[9].
It has been reported that large and medium pore supports
display higher activities compared to smaller pore size ones
[16]. However, we found that using large pore Al2O3 as
supports decreased the conversion of hydrogenation of
MA. This may be due to the different reaction mechanism
here, with the SA formed mainly by the MA hydrogenation
over metal rather than the supports.
3.2 Catalytic Activity
Preliminary investigations were carried out on the effect of
various reaction parameters on the hydrogenation of MA to
optimize the reaction conditions.
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J. Li et al.
Table 1 Catalytic properties
Samples
Conversion of maleic
anhydride (%)
Selectivity
(%) SA
Selectivity
(%) GBL
of studied catalysts
5%Ni/HX–Al2O3
5%Ni/USY-Al2O3
5%Ni/ZSM-5-Al2O3
5%Ni/Beta-Al2O3
5%Ni/HY–Al2O3
5%Ni/Al2O3
89.61
34.62
68.71
12.76
90.24
65.37
99.84
95.48
93.69
37.45
99.89
85.56
64.40
56.16
65.67
29.40
82.87
64.19
86.92
67.60
72.04
34.11
91.93
75.61
35.60
43.84
34.33
70.60
17.13
35.81
13.08
32.40
27.96
65.89
8.07
5%Ni–0.5%Pt/HX–Al2O3
5%Ni–0.5%Pt/USY-Al2O3
Reaction conditions:
5%Ni–0.5%Pt/ZSM-5-Al2O3
WHSV = 2 h-1 maleic
anhydride, reaction
pressure = 1 MPa, reaction
temperature = 140 °C,
H2/MA = 50 (molar ratio)
5%Ni–0.5%Pt/Beta-Al2O3
5%Ni–0.5%Pt/HY–Al2O3
5%Ni–0.5%Pt/Al2O3
34.39
3.2.2 Effect of Reaction Temperature
of the MA hydrogenation is formation of GBL rather than
SA [10]. However, the rate of reaction was lower than for
the composite system at 150 °C, and complete conversion
could be reached after 4 h run time, instead of the 3 h on the
stream needed for the latter. It is apparent from the results
that the desired product selectivity can be obtained by
controlling the temperature.
Reactions were carried out at 120–150 °C (Fig. 4). As
expected, the rate of conversion of MA increased as
increased the reaction temperature. Temperature was criti-
cal in controlling the desired production selectivity. The
conversion of maleic anhydride increased from 85 to 100%
after 4 h reaction time on increasing the reaction tempera-
ture from 120 to 140 °C. This could be the result of NiPt
being a good bimetallic hydrogenation catalyst. SA yield/
selectivity decreased with increasing in the reaction tem-
perature from 140 to 150 °C. A high SA yield could be
obtained at 140 °C. In agreement with the results shown
here, previous studies have reported that at higher temper-
ature, over-hydrogenated reaction occurred, the production
3.2.3 Effect of Reaction Pressure
The effect of H2 pressure on the maleic anhydride hydro-
genation (Fig. 5) shows that 100% MA conversion with
more than 97% selectivity to SA could be obtained at
140 °C and at a pressure of 0.8 MPa H2. Product conver-
sion and selectivity, however, varies significantly with
changes in pressure (Fig. 5). It is seen that SA selectivity
100
80
100
80
60
120
130
40
140
150
20
0
60
1
2
3
4
5
6
7
MA conversion
SA Selectivity
100
90
80
70
60
50
40
30
20
40
120
130
140
150
20
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1
2
3
4
5
6
7
Time (h)
Pressure (MPa)
Fig. 4 Hydrogenation of maleic anhydride over 5%Ni–0.5%Pt/HY–
Al2O3: effect of reaction temperature; reaction conditions:
WHSV = 2 h-1 maleic anhydride, reaction pressure = 1 MPa,
H2/MA = 50 (molar ratio)
Fig. 5 Hydrogenation of maleic anhydride over 5%Ni–0.5%Pt/HY–
Al2O3: effect of reaction pressure; reaction conditions:
WHSV = 2 h-1 maleic anhydride, reaction temperature = 140 °C,
H2/MA = 50 (molar ratio)
123