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Catalysis Communications 10 (2009) 592–595

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Catalysis Communications
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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,*
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
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.
Ó 2008 Elsevier B.V. All rights reserved.
Selective hydrogenation
Maleic anhydride
Supercritical carbon dioxide
Phase behavior

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

ing environmental and process advantages [18,19]. Pillai et al.
Hydrogenation of maleic anhydride (MAH) is an important [20,21] reported that the hydrogenation of MAH over Pd/Al2O3
industrial chemical process, since all the hydrogenation products, could be performed in scCO2 and the selectivity to GBL was en-
e.g. succinic anhydride (SAH), c-butyrolactone (GBL), 1,4-butane- hanced compared to that in organic solvents. They found that all
diol (BDO) and tetrahydrofuran (THF), are important intermediates the MAH could dissolve in the scCO2 phase at pressures of
or solvents in food, pharmaceuticals and textile industries [1–6]. 2.1 MPa H2 and 12 MPa CO2, at 200 °C, and complete conversion
The hydrogenation of MAH is generally carried out in gas or liquid of MAH with 80% selectivity to GBL was obtained under the condi-
phase over noble metal catalysts [7–10] or oxide supported metal tions. Compared with the heterogeneous reaction, the homoge-
catalysts [11–14]. Lu et al. [12] reported that Al2O3 supported Cu neous reaction in scCO2 presented more merits for that all the
catalyst modified with TiO2 exhibited higher selectivity for GBL substrates and catalyst could completely dissolved in scCO2 phase
in the gas phase hydrogenation of MAH. Hydrogenation of MAH forming a single phase, in which all the mass transfer resistance
was mainly studied in organic solvents such as ethylene glycol di- disappeared. In the present study, hydrogenations of MAH and
methyl ether (EGDME) and polyethylene glycol dimethyl ether SAH catalysed with homogeneous catalyst of Dichlorotetrakis(tri-
(PEGDME), which are toxic, preventing their application in indus- phenylphosphine)ruthenium(II) (RuCl2(TPP)3) complex in scCO2
trial scale. Recently, supercritical carbon dioxide (scCO2) was used were investigated. Parameters such as temperature, pressure and
as replacement for conventional organic solvents, due to its low- reaction time were examined. The extremely improvement in
cost, environmentally benign, non-toxic, and non-flammable nat- product selectivity in scCO2 were discussed in detail.
ure. ScCO2 also exhibits desirable characteristics such as the
adjustable solvent properties [15–17]. Generally, the rate of cata- 2. Experimental section
lytic hydrogenation in liquid phase is low due to the low solubility
of gaseous hydrogen in common solvents. In contrast, hydrogen is The hydrogenation of MAH was carried out in a 50 ml stainless
completely miscible with scCO2. The resultant enhancement in steel batch reactor with RuCl2(TPP)3 catalyst, which was prepared
hydrogen concentration can lead to an increase in reaction rate. under nitrogen atmosphere as described in literature [22], and
Thus the use of scCO2 as solvent in hydrogenation promises to 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
* Corresponding author. Tel./fax: +86 431 85262410. into the reactor. The reactor was then sealed and flushed three
E-mail address: (F. Zhao). 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.
Q. Wang et al. / Catalysis Communications 10 (2009) 592–595 593

Fig. 1. FTIR spectra of RuCl2(TPP)3 complex.

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

Scheme 1. Hydrogenation of MAH.

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.
In the presence of 14 MPa CO2.
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.

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-
Fig. 4. Influence of CO2 pressure on hydrogenation of MAH in scCO2. Reaction
tained in scCO2 (entries 9–11 in Table 1), in which the hydrogena-
conditions: MAH 5 mmol, catalyst RuCl2(TPP)3 0.02 mmol, H2 4 MPa, temperature tion occurred mainly in homogeneous CO2 phase, all the SAH and
200 °C, reaction time 2 h. 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.


The authors gratefully acknowledge to the financial support

from the One Hundred Talent Program of CAS.


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