Catalysis Today 212 (2013) 137–141
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
Synthesis of succinic anhydride from maleic anhydride on Ni/diatomite catalysts
∗
Shaofei Guo, Li Shi
The State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
The characteristics and catalytic properties of Ni(5 wt%)/diatomite, Ni(5 wt%)/␥-Al O , Ni(5%
2
3
Received 18 January 2012
Received in revised form 21 August 2012
Accepted 3 October 2012
wt)/Bentonite clay and Ni(5 wt%)/attapulgite clay were investigated and compared in terms of catalytic
activities for liquid-phase hydrogenation of maleic anhydride (MA). The results showed that the diatomite
support exhibited the highest activity and selectivity. Using Ni(7 wt%)/diatomite catalyst, the 100% con-
Available online 11 November 2012
◦
version of MA and 96.20% selectivity to SA were obtained for MA hydrogenation at 190 C. The X-ray
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diffraction (XRD) studies showed that there is only NiO on the support and no elemental nickel (Ni )
Keywords:
and Ni2O3 was detected in unreduced samples. XRD and H2 temperature-programmed reduction (TPR)
Maleic anhydride
Hydrogenation
Succinic anhydride
Diatomite
0
◦
studies also showed that NiO species were all converted to metallic nickel (Ni ) after reduction at 350 C.
© 2012 Elsevier B.V. All rights reserved.
1
. Introduction
Catalytic hydrogenation of maleic anhydride (MA) produces
The use of different catalysts, based on both noble and nonno-
ble metals, was reported in the literature for the hydrogenation
of MA. It was reported that the noble metal-based catalysts,
such as Pd/SiO2 [5], Pd/TiO2 [6], Pd–Sn/SiO2 [5], were stud-
ied in liquid phase. Generally, the experiments were carried
important industrial chemicals, such as succinic anhydride (SA)
and ␥-butyrolactone (GBL), 1,4-butanediol (BDO) and tetrahydro-
furan (THF), which are widely used in polymer and pharmaceutical
industries [1]. In particular, SA is required as intermediate for the
chemical, pharmaceutical and food industries [2].
SA are produced by two main processes: dehydration of succinic
acid process and hydrogenation of MA process [3]. The liquid-phase
catalytic hydrogenation of MA to SA has attracted increasing atten-
tion because of the simple process and the low-cost raw material
of MA which due to the large-scale industrialization and great
improvement of the technology of oxidation of n-butane to MA.
The hydrogenation of MA is an alternative to dehydration of suc-
cinic acid process, in viewpoint of cost lowering and environmental
protection.
◦
out in the temperature and pressure ranges of 200–240 C and
1–5 MPa, GBL was dominantly formed. In order to avoid the
utilization of expensive noble metal catalysts, copper-based cat-
alysts were investigated in hydrogenation of MA. Copper-based
catalysts, such as Cu–ZnO–MgO–Cr O3 [7], Cu–ZnO–TiO2 [8],
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Cu–ZnO–ZrO /H-Y [9], Cu–ZnO–CeO2 [10], Cu–ZnO–Zr [11] and
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Cu–Pd(Ni)–TiO –Al O [12], were also used to study the gas- and
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2
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liquid- phase hydrogenation of MA at temperature between 210
◦
and 280 C at pressure between 0 and 5 MPa. But there are still some
disadvantages over those catalysts, such as higher reaction temper-
ature, lower liquid hourly space velocity (WHSV) of raw material,
higher H /MA molar ratio, lower selectivity of SA, and poisonous
2
The reaction network for the MA hydrogenation is rather com-
plex and different type of reactions can occur, depending on the
catalyst and reaction conditions. In a first step, the hydrogenation
of the C C bond in MA produces SA. Then, the hydrogenolysis
of one C O bond in SA gives GBL. Finally, THF and BDO can be
obtained by GBL hydrogenolysis. Other hydrogenolysis reactions
can also produce C4 and C3 compounds, such as n-butanol, n-
propanol, butyric acid and propionic acid. The reaction network
composition of Cr in the catalyst.
Supported Ni catalysts are widely used in liquid-phase hydro-
genation for many important organic transformations. Therefore,
supported Ni catalyst was chosen to investigate MA hydrogena-
tion for its widely using and low cost. It is known that a support
can affect catalyst activity, selectivity, recycling, refining, materials
handling, and reproducibility. Common catalyst supports include
activated carbons [13], silicas [14], aluminas [15], and to a lesser
extent, polymers [16] and zeolites [17]. In this study, the conversion
of MA and the selective hydrogenation of MA to SA were investi-
gated on supported Ni catalysts: Ni(5% wt)/attapulgite clay (Ni5/At),
Ni(5 wt%)/bentonite clay (Ni5/Be), Ni(5 wt%)/␥-Al O (Ni5/Al) and
2
3
∗ Corresponding author. Tel.: +86 21 64252274; fax: +86 21 64252386.
Ni(5 wt%)/diatomite (Ni5/Di). The results showed that Ni5/Di has
the best performance for hydrogenation of MA. Moreover, the
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