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Abstract
Gas-phase dehydration of glycerol to produce acrolein was investigated at 315 ◦ C over Nb2 O5 catalysts calcined in the temperature range of
350–700 ◦ C. The catalysts were characterized by nitrogen physisorption, TG-DTA, XRD, and n-butylamine titration using Hammett indicators to
gain insight into the effect of calcination temperature on catalyst texture, crystal structure, and acidity. Calcination at 350 and 400 ◦ C produced
amorphous Nb2 O5 catalysts that exhibit significantly higher fractions of strong acid sites at −8.2 H0 −3.0 (H0 being the Hammett acidity
function) than the crystallized Nb2 O5 samples obtained by calcination at or above 500 ◦ C. Glycerol conversion and acrolein selectivity of the
Nb2 O5 catalysts were dependent of the fraction of strong acid sites (−8.2 H0 −3.0). The amorphous catalyst prepared by the calcination
at 400 ◦ C, having the highest fraction of acid sites at −8.2 H0 −3.0, showed the highest mass specific activity and acrolein selectivity
(51 mol%). The other samples, having a higher fraction of either stronger (H0 −8.2) or weaker acid sites (−3.0 H0 6.8), were less
effective for glycerol dehydration and formation of the desired acrolein.
© 2007 Elsevier Inc. All rights reserved.
Keywords: Niobium oxide (Nb2 O5 ); Solid acid; Glycerol (glycerin); Acrolein; Alcohol dehydration; Sustainable technology
1. Introduction (SPA), have been tested for the dehydration of glycerol in either
gaseous or liquid phases [9–11]. The dehydration of glycerol
The use of renewable resources, such as biomass, as feed- also has been investigated in sub-supercritical and supercritical
stock for the production of fuels and chemicals has become water (250–390 ◦ C and 25–35 MPa) in the presence of low con-
an increasingly important focus in energy-related catalysis, be- centrations of liquid acids or salts [12–14]. Glycerol is usually
cause fossil resources will be exhausted in a few decades [1–4]. produced as a mixture with water. The direct use of glycerol in
Glycerol is a main byproduct in natural triglyceride methanoly- water is advantageous over pure glycerol for the production of
sis for biodiesel production. In recent years, the increasing use acrolein, but a highly water-tolerant solid acid catalyst would
and production of biodiesel has resulted in an increase of glyc- be developed for the purpose.
erol production and a price decline, which makes glycerol a Niobium oxide (Nb2 O5 ) has been used as a water-tolerant
particularly attractive molecule (building block) for the synthe- solid acid catalyst for various water-involving reactions, such as
sis of other valuable chemical products [5–8]. Catalytic conver- esterification, hydrolysis, dehydration, and hydration [15–18].
sion of glycerol to acrolein by a double-dehydration reaction A key to the acidic and catalytic properties of Nb2 O5 is its calci-
(Fig. 1) could be an important route for using glycerol resources nation or pretreatment temperature [19]. In this paper we report
and could offer a sustainable alternative to the present acrolein our investigation into the catalytic behavior of Nb2 O5 catalysts
technology based on propylene. Various solid acid catalysts, in- prepared by varying the calcination temperature of a hydrated
cluding sulfates, phosphates, zeolites, and solid phosphoric acid niobium oxide (Nb2 O5 ·nH2 O) for the gas-phase dehydration
of aqueous glycerol. Our data provide a basis for correlating
* Corresponding author. Fax: +86 10 62792122. the catalyst acidity with the catalytic performance in glycerol
E-mail address: bqxu@mail.tsinghua.edu.cn (B.-Q. Xu). dehydration.
0021-9517/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcat.2007.06.016
S.-H. Chai et al. / Journal of Catalysis 250 (2007) 342–349 343
Table 1
Texture properties of calcined Nb2 O5 catalysts
Calcination BET surface Pore volumea Average pore diameter (nm)
temperature area (cm3 g−1 ) BJH adsorption BJH desorption
(◦ C) (m2 g−1 )
350 115 0.14 5.1 4.7
400 99 0.13 5.6 5.0 Fig. 3. (A) TG-DTG and (B) DTA curves of the hydrated niobium oxide.
500 42 0.11 10.3 8.0
600 12 0.05 21.1 16.6
700 7 0.03 20.7 22.0
a Measured at P /P = 0.995.
0
volume (from 0.14 to 0.03 cm3 g−1 ), which were especially re-
markable when the calcination was done at temperatures above
400 ◦ C. The average pore diameter, ca. 5 nm for the samples
calcined at 350 and 400 ◦ C, also increased remarkably after
calcination at 500–700 ◦ C. The surface area data agree well
with those reported by Tanabe et al. [23], whose data were
126 m2 g−1 after the evacuation at 300 ◦ C and 42 m2 g−1 af-
ter evacuation at 500 ◦ C.
3.3. Catalyst acidity only over the sample calcined at 350 ◦ C. The fraction of strong
acid sites (−8.2 H0 −3.0) was as high as 0.6 (i.e., 60% of
Based on their acid strength, acid sites at the catalyst sur- the total acidity) over the catalyst calcined at 400 ◦ C. The frac-
face are divided into the following three groups: medium-strong tion of medium-strong to weak acid sites (−3.0 H0 6.8)
and weak (−3.0 H0 6.8), strong (−8.2 H0 −3.0), increased with increasing catalyst calcination temperature.
and very strong (H0 −8.2). The total amount of acid sites
in the three groups is defined as the total acidity (H0 6.8). 3.4. Catalytic reaction
Fig. 5 shows the effect of calcination temperature on the acidity
and acid site distribution of the Nb2 O5 catalysts. The high- The catalytic dehydration of glycerol over the present
est acid strength of Nb2 O5 samples decreased with increas- Nb2 O5 catalysts was characterized by a decrease in the con-
ing calcination temperature (T ): H0 −8.2 for T = 350 ◦ C, version of glycerol with the reaction time on stream (TOS),
−8.2 H0 −3.0 for T = 400–600 ◦ C, and −3.0 H0 along with an induction period to reach a stable selectivity
6.8 for T = 700 ◦ C. The increase in the calcination tempera- for acrolein production. Examples are shown in Fig. 7. With
ture also reduced the catalyst acidity (amounts) in the differ- the catalysts calcined at 400 and 700 ◦ C, glycerol conversion
ent acid strength ranges. These acidity data (acid strength and decreased with TOS but the selectivity for acrolein increased
amount) are quite similar to those obtained by Tanabe et al. on during the first 3–6 h and stabilized at longer TOS. Thus, cat-
Nb2 O5 samples pretreated/calcined at comparable temperatures alytic reaction data at TOS of 1–2 and 9–10 h are presented in
[23,24]. Fig. 8 to show the effect of calcination temperature on the cat-
Fig. 6 gives the fraction of acid sites with different acid alytic performance of Nb2 O5 . The catalyst calcined at 400 ◦ C
strengths. Very strong acid sites (H0 −8.2) were observed exhibited the highest selectivity (up to 51 mol% by normal-
ization to glycerol reacted (Fig. 8B)) for acrolein production;
despite this, the glycerol conversion based on the catalyst vol-
ume (0.63 ml) was slightly lower over this catalyst than over
the catalyst calcined at 500 ◦ C (Fig. 8A).
The effect of calcination temperature on the stabilized prod-
uct distribution (i.e., 9–10 h TOS) is shown in Table 2. In
addition to the desirable acrolein, the main product from the
Fig. 6. Effect of the calcination temperature on the fraction of acid sites at (!)
H0 −8.2, (2) −8.2 H0 −3.0, and (P) −3.0 H0 6.8 over Nb2 O5 Fig. 7. Time courses of (2) glycerol conversion and (1) acrolein selectivity
catalyst. over Nb2 O5 catalysts calcined at (A) 400 and (B) 700 ◦ C.
346 S.-H. Chai et al. / Journal of Catalysis 250 (2007) 342–349
Table 2
Effect of calcination temperature on product distribution over Nb2 O5 catalysts (TOS = 9–10 h)
Calcination tem- Conversion Product selectivity (mol%)
perature (◦ C) (%) Acrolein Acetaldehyde Propionaldehyde Acetone Allyl alcohol 1-Hydroxylacetone Othersa
350 75 47 4.7 2.9 3.1 1.3 10 31.0
400 88 51 4.1 2.4 2.4 1.4 12 26.7
500 92 35 5.3 3.2 3.2 2.3 14 37.0
600 76 33 2.7 1.1 1.1 2.9 21 38.2
700 32 28 1.8 0.4 0.5 5.4 19 44.9
a Selectivity for others (mol%) = 100 − total selectivity for all products identified.
S.-H. Chai et al. / Journal of Catalysis 250 (2007) 342–349 347
Fig. 11. Areal catalytic rates of Nb2 O5 catalysts for (P) glycerol consumption
and (2) acrolein formation at TOS = 9–10 h.
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