Catalysis Communications 10 (2009) 592–595

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Selective hydrogenation of maleic anhydride to c-butyrolactone

in supercritical carbon dioxide
Qiang Wang a,b, Haiyang Cheng a,b, Ruixia Liu a,b, Jianmin Hao a,b, Yancun Yu a, Shuxia Cai a, Fengyu Zhao a,*
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The reaction rates of the hydrogenation of maleic anhydride (MAH) and succinic anhydride (SAH) were
Received 1 August 2008 significantly accelerated and the selectivity to c-butyrolactone (GBL) was enhanced largely when the
Received in revised form 30 October 2008 reaction mixture was pressurized by a non-reactant of CO2. Above 99% selectivity to GBL was achieved
Accepted 30 October 2008
in 14 MPa CO2, the superior selectivity in scCO2 was attributed to that MAH and/or SAH could be
Available online 13 November 2008
extracted to CO2 phase and separated from H2O, the hydrolysis were thus minimized and so the selectiv-
ity to GBL was improved.
Keywords:
Ó 2008 Elsevier B.V. All rights reserved.
Selective hydrogenation
Maleic anhydride
c-Butyrolactone
Supercritical carbon dioxide
Phase behavior

1. Introduction overcome the drawbacks of conventional organic solvents by offer-

Hydrogenation of maleic anhydride (MAH) is an important
industrial chemical process, since all the hydrogenation products,
e.g. succinic anhydride (SAH), c-butyrolactone (GBL), 1,4-butane-
diol (BDO) and tetrahydrofuran (THF), are important intermediates
or solvents in food, pharmaceuticals and textile industries [1–6].
The hydrogenation of MAH is generally carried out in gas or liquid
phase over noble metal catalysts [7–10] or oxide supported metal
catalysts [11–14]. Lu et al. [12] reported that Al2O3 supported Cu
catalyst modified with TiO2 exhibited higher selectivity for GBL
in the gas phase hydrogenation of MAH. Hydrogenation of MAH
was mainly studied in organic solvents such as ethylene glycol di-
methyl ether (EGDME) and polyethylene glycol dimethyl ether
(PEGDME), which are toxic, preventing their application in indus-
trial scale. Recently, supercritical carbon dioxide (scCO2) was used
as replacement for conventional organic solvents, due to its low-
cost, environmentally benign, non-toxic, and non-flammable nat-
ure. ScCO2 also exhibits desirable characteristics such as the
adjustable solvent properties [15–17]. Generally, the rate of cata-
lytic hydrogenation in liquid phase is low due to the low solubility
of gaseous hydrogen in common solvents. In contrast, hydrogen is
completely miscible with scCO2. The resultant enhancement in
hydrogen concentration can lead to an increase in reaction rate.
Thus the use of scCO2 as solvent in hydrogenation promises to
* Corresponding author. Tel./fax: +86 431 85262410.
E-mail address: zhaofy@ciac.jl.cn (F. Zhao).
ing environmental and process advantages [18,19]. Pillai et al.
[20,21] reported that the hydrogenation of MAH over Pd/Al2O3
could be performed in scCO2 and the selectivity to GBL was en-
hanced compared to that in organic solvents. They found that all
the MAH could dissolve in the scCO2 phase at pressures of
2.1 MPa H2 and 12 MPa CO2, at 200 °C, and complete conversion
of MAH with 80% selectivity to GBL was obtained under the condi-
tions. Compared with the heterogeneous reaction, the homoge-
neous reaction in scCO2 presented more merits for that all the
substrates and catalyst could completely dissolved in scCO2 phase
forming a single phase, in which all the mass transfer resistance
disappeared. In the present study, hydrogenations of MAH and
SAH catalysed with homogeneous catalyst of Dichlorotetrakis(tri-
phenylphosphine)ruthenium(II) (RuCl2(TPP)3) complex in scCO2
were investigated. Parameters such as temperature, pressure and
reaction time were examined. The extremely improvement in
product selectivity in scCO2 were discussed in detail.
2. Experimental section
The hydrogenation of MAH was carried out in a 50 ml stainless
steel batch reactor with RuCl2(TPP)3 catalyst, which was prepared
under nitrogen atmosphere as described in literature [22], and
transmittance at 1493 and 1440 cm 1 as shown in Fig. 1 are charac-
teristic peaks of RuCl2(TPP)3. RuCl2(TPP)3 and MAH were loaded
into the reactor. The reactor was then sealed and flushed three
times with 1 MPa N2. After the reactor was heated up to the reaction

1566-7367/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.10.042
 Q. Wang et al. / Catalysis Communications 10 (2009) 592–595
Fig. 1. FTIR spectra of RuCl2(TPP)3 complex.
temperature of 200 °C, first H2 and then CO2 were introduced into
the reactor to the desired pressure using a high-pressure liquid
pump. The reaction mixture was stirred continuously with a Tef-
lon-coated magnetic stir bar with a stirring speed around
1300 rpm. Upon completion of the reaction the reactor was cooled
to room temperature and depressurized carefully with a back-pres-
sure regulator. The liquid mixture was diluted with acetone. The
products were analyzed by gas chromatography (GC-Shimadza-
14C, FID, Capillary column, Rtx-Wax 30 m  0.53 mm  0.25 mm)
and gas chromatography/mass spectrometry (GC/MS, Agilent
5890).
An 80 ml high-pressure sapphire-windowed reactor was used
to examine the phase behavior. MAH (8 mmol) or SAH (3.53 mmol)
were added into the reactor and then the reactor was sealed and
flushed three times with 1 MPa N2. After the reactor was heated
up to 200 °C H2 was introduced into the reactor and then CO2
was filled up to the desired total pressure, ranging from 0 to
20 MPa. The mixture was maintained at a certain pressure for sev-
eral minutes while stirring, then stop the stirring and the state of
mixture was observed by the naked eye from the window.
3. Results and discussion
3.1. Hydrogenation of MAH
The hydrogenation of MAH produces several products as shown
in Scheme 1. The influence of temperature on hydrogenation of
MAH in scCO2 is shown in Fig. 2. The results indicated that temper-
ature was an important factor in controlling the product distribu-
Scheme 1. Hydrogenation of MAH.
593
Fig. 2. Influence of temperature on hydrogenation of MAH in scCO2. Reaction
conditions: MAH 5 mmol, catalyst RuCl2(TPP)3 0.02 mmol, H2 4 MPa, CO2 14 MPa,
reaction time 2 h.
tion. GBL could be selectively produced with a yield of 84% at
200 °C, while SAH instead of GBL was the main product at
160 °C. Similar results were reported in the MAH hydrogenation
with Pd–Ni–Mo/SiO2 catalyst [10].
It was found that the yield of GBL increased with increases of
reaction time in all the solvents used as shown in Fig. 3. The GBL
yield increase in scCO2 was observed in the initial 2 h, plateauing
at 84%, which is higher than those obtained in EGDME and sol-
vent-free conditions. A relatively high initial yield was observed
in EGDME, possibly due to the high solubility of MAH in this sol-
vent. But, in the case of solvent-free, GBL formed during the hydro-
genation could act as co-solvent to dissolve MAH and SAH, leading
to a gradual enhancement of the reaction rates, especially for that
of the second step from SAH to GBL. In the case of scCO2, the initial
yield of GBL was a little lower than that in EGDME, but it increased
very fast when the dissolving equilibrium (MAH to scCO2 phase)
reached. In the MAH hydrogenation, a side-product of succinic acid
(SA) was formed from the hydrolysis of SAH because an equivalent
amount of H2O was produced during the hydrogenation, which is
in agreement to the results of the SAH hydrogenation with ruthe-
nium complexes in several organic solvents [7]. The yield of GBL
was the highest in scCO2. And the presence of CO2 could increase
the selectivity of GBL in EGDME as well. In pure EGDME and sol-
vent-free conditions, a large amount of side-products were pro-
duced, indicating that the presence of CO2 could improve the
hydrogenation of SAH to GBL, which will be discussed with phase
behavior later.
594 Q. Wang et al. / Catalysis Communications 10 (2009) 592–595

Table 1
Results for the hydrogenation of SAH with RuCl2(TPP)3 complex in scCO2 and EGDME.

Entry SAH Time Conversion Selectivity (%) Phase

(mmol) (h) (%) GBL SA
In 2 ml EGDME
1 5 1 29 43 57 g-l
2 5 2 40 53 47 g-l
3 5 3 49 64 36 g-l
4a 5 1 43 90 10 g-l
5b 5 1 88 — 93 g-l
In 14 MPa CO2
6 5 1 47 80 20 g-l
7 5 2 57 81 19 g-l
8 5 3 60 91 9 g-l
9 2.5 1 74 96 4 gc
10 2.5 2 82 97 3 g
11 2.5 3 87 99 1 g
Fig. 3. Time dependence of the yield of SAH and GBL in hydrogenation of MAH.
12d 2.5 1 77 73 27 g-l
Reaction conditions: MAH 5 mmol, catalyst RuCl2(TPP)3 0.02 mmol, H2 4 MPa, CO2
14 MPa, EGDME 2 ml, temperature 200 °C. Reaction conditions: reaction temperature 200 °C, amount of catalyst RuCl2(TPP)3
0.002 mmol.
a
In the presence of 14 MPa CO2.
b
The reaction was performed in a mixed solvent of 2 ml EGDME and 0.5 ml H2O.
CO2 pressure had a significant effect on product distribution in c
All the substrates dissolved into scCO2 phase, very little amount of Ru complex
the hydrogenation of MAH, as shown in Fig. 4, in which the product precipitated on the bottom of reactor.
distribution was compared after reaction for 2 h at 100% conver- d
The reaction was performed in 6 MPa CO2 instead of 14 MPa CO2.
sion of MAH. The yield of GBL increased with increasing CO2 pres-
sure, a GBL yield from 36 to 84%, was observed when CO2 pressure
was increased from 0 to 14 MPa. This may be attributed to the
SAH to GBL was examined as shown in Table 1. The conversion
changes in phase behavior and molecular interactions among sub-
and selectivity to GBL increased with increasing reaction time in
strate, catalyst and CO2 molecules. At 14 MPa CO2, the reaction was
both the EGDME and 14 MPa CO2. When the hydrogenation of
mainly performed in the homogeneous phase as all the substrates
SAH was performed in EGDME, the selectivity to GBL was lower
as well as a large amount of catalyst were dissolved in CO2. More-
than 65% for that large amount of SA (>35% in selectivity) was
over, favorable molecular interactions may exist in the scCO2
formed as a side-product (entries 1–3). However, when the hydro-
phase, affecting the reaction rate and product selectivity as dis-
genation of SAH in pure EGDME was compressed with 14 MPa CO2,
cussed in the literature [23–25]. However, when a large amount
both the conversion and selectivity of GBL was improved largely,
of CO2 was introduced, the dilution effect might counterbalance
they are increased from 29 to 43% and 43 to 90%, respectively (en-
the favorable effects of homogenous phase and potential interac-
tries 1, 4). However, when a little amount of water was added to
tion between MAH and CO2, and so the yield of GBL presented a de-
the reaction in EGDME, GBL was not detected in the products in-
crease at the higher CO2 pressure of 16 MPa.
stead of a quantity of SA was formed from the hydrolysis of SAH
(entry 5). It is worth to note that the reaction rate and GBL selec-
3.2. Hydrogenation of SAH
tivity are higher in 14 MPa CO2 than those in EGDME. The conver-
sion reached about 47% in 14 MPa CO2 (entry 6), but it was only
The hydrogenation of MAH contains several reaction steps as
about 29% in EGDME (entry 1) under the same reaction conditions.
described above, in which C@C bond was first hydrogenated to
In addition, the selectivity of GBL is much higher in scCO2 and it
SAH quickly even at the moderate temperatures, but from SAH to
reached 99% at the optimum reaction conditions (entry 11). But
GBL through a C@O bond hydrogenation is difficult and it should
when the hydrogenation was carried out in 6 MPa CO2 (subcritical
perform at a temperature above 200 °C. In order to compare the
conditions), the selectivity of GBL decreased to 73%, and 27% of SA
activity of RuCl2(TPP)3 in different solvents, the hydrogenation of
was produced. These could be explained from the phase behavior
as discussed below.

3.3. Influence of phase behavior

The phase behavior was observed for SAH in compressed CO2.

Fig. 4. Influence of CO2 pressure on hydrogenation of MAH in scCO2. Reaction
conditions: MAH 5 mmol, catalyst RuCl2(TPP)3 0.02 mmol, H2 4 MPa, temperature
200 °C, reaction time 2 h.
As the pictures shown in Fig. 5, the solubility of SAH increased with
increasing CO2 pressure and a homogeneous phase presented at
pressures of 10–12 MPa in pure CO2. By contrast, in the presence
of 4 MPa H2, the formation of homogeneous phase moved to higher
pressures of 12–14 MPa, suggesting that the solubility of SAH in
compressed CO2 decreased in the presence of H2, which is in agree-
ment to the literature [26]. In the SAH hydrogenation, SA was usu-
ally produced from the hydrolysis of SAH under the reaction
conditions. However, when the reaction was performed in the
presence of compressed CO2, the hydrolysis of SAH was restrained
for that SAH was dissolved into CO2 phase completely and isolated
from the water. Therefore, high selectivity to GBL (>96%) was ob-
tained in scCO2 (entries 9–11 in Table 1), in which the hydrogena-
tion occurred mainly in homogeneous CO2 phase, all the SAH and
large amount of Ru complex catalyst dissolved into the CO2 phase,
 Q. Wang et al. / Catalysis Communications 10 (2009) 592–595 595

4. Conclusions

The hydrogenations of MAH and SAH to GBL have been per-

formed selectively in scCO2 in the present work. The total conver-
sion and selectivity for GBL in scCO2 are higher than those obtained
in organic solvent of EGDME. A high selectivity of 99% was ob-
tained for SAH hydrogenation in 14 MPa CO2 under the optimum
conditions. The superior selectivity was attributed to the phase
behavior changes in scCO2, at high CO2 pressure, MAH and/or
SAH could be extracted into CO2 phase and separated from H2O
formed during hydrogenation, the side-product from the hydroly-
sis of MAH or SAH was thus minimized in compressed CO2 result-
ing in an enhancement in the selectivity to GBL.

Acknowledgements

The authors gratefully acknowledge to the financial support

from the One Hundred Talent Program of CAS.

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