Jointlypublished by Elsevier ScienceB.V.

, Amsterdam and Akad6miaiKiad6, Budapest

React.Kinet.Catal.L~. Vol. 65, No. 1, 83-86 (1998)

RKCL3184
BASICITIES OF ALUMINA-SUPPORTED ALKALINE EARTH METAL OXIDES Yu-Wen Chen', Hsueh-Ying Chen b and Wen-Fa Lin b
aDepartment of Chemical Engineering, National Central University Chtmg-Li 32054 Taiwan bUnion Chemical Laboratory, Industrial Technology Research Institute Hsinchu 30042 Taiwan

Received October 28, 1998 In revised form March 25, 1998 Accepted June 19, 1998 Abstract
A series of alumina-supported alkaline earth metal oxide catalysts were prepared by recipient-wetness impregnation. These catalysts were characterized by nitrogen-sorption to determine their surface areas and pore size distributions. The basicities of these catalysts were characterized by temperature-programmed des0rption of carbon dioxide. The TPD results demonstrate that all of the catalysts have one-peak profiles. The basicity increases with increasing atomic number of the alkaline earth metal. The alumina-supported alkaline earth oxides exhibit the same basic properties as bulk metal oxides. However, the presence of alumina can increase the mechanical strength of the catalyst, since the alkaline earth oxides have a weak mechanical strength. The basic properties of the catalysts are strongly influenced by the calcination temperature.

Keywords: Alkaline earth oxide, basicity, temperature-programmed, desorption of carbon dioxide

INTRODUCTION

Alkaline earth metal oxides have long been known as basic solid catalytic materials [1]. In contrast to extensive studies of solid acid catalysts, little attention has given to the studies of solid base catalysts. It has been revealed that not only single component metal oxides but also alkaline earth modified oxides and alkaline earth ion exchanged zeolite exhibit basic properties on the surface [2-3]. In addition to being an application of solid base-catalyzed reaction, the
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YU-WEN-CHENet al.: BASIC1TIES

elucidation of basic properties of catalysts becomes more important in the design of advanced catalysts. In this study, a series of alumina-supported alkaline earth metal oxides were prepared. The basic properties of these catalysts were characterized by temperature-programmed desorption of carbon dioxide. EXPERIMENTAL The 7-alumina used for the support was supplied from Jansen Chemicals. All of the alkaline earth metal nitrates were from Merck Chemicals. The alumina-supported alkaline earth metal oxides were prepared by incipient-wetness impregnation of 7-A1203 with aqueous solutions of alkaline earth nitrates. The samples were dried at 100~ for 12 h, followed by calcination at 550~ for 6 h in air, if not specified. The contents of alkaline earth metal oxides were 20 wt.%. The surface areas and pore diameters of there catalysts were determined by nitrogen adsorption using Micromeritics ASAP 2000. To examine the amount and strength of basic sites on the surface of catalysts, temperature-programmed desorption (TPD) analysis for the adsorbed carbon dioxide was carried out. A catalyst (0.5 g) calcined at a certain pretreatment temperature for 2 h was exposed to 50 kPa of CO2 at room temperature for 10 min followed by flowing argon at room temperature for 30 min. The TPD was run at a heating rate of 10 K/min from room temperature to 800~ The desorbed gas was analyzed with a thermal conductivity detector.
Table 1

The specific surface areas of the catalysts

Catalyst Surface area (m2/g)

A1203 MgO/A1203 CaO/A1203 SrO/A1203 BaO/A1203

180 130 136 142 151

RESULTS AND DISCUSSION The specific surface areas of the catalysts are given in Table 1. It is well known that the surface areas of alkaline earth oxides vary with the pretreatment temperature. In the present study, all of the catalysts were pretreated at 550~ The specific surface areas of the catalysts decreased upon an addition of alkaline

YU-WEN-CI-IENet al.: BASICrrIES

85

earth oxides, as shown in Table 1. In the XRD pattems of the catalysts, both the y-A1203 and alkaline earth oxide phases were observed, Furthermore, an addition of alkaline earth oxide does not provoke any considerable changes in the y-A1203 texture. The TPD spectra of carbon dioxide adsorbed on the catalysts are shown in Fig. 1. In TPD of the adsorbed CO2, the concentration of the basic sites is reflected in the peak of TPD plot, and in the strength of the basic sites at the temperature at which CO2 desorption peak appears. Since acidic carbon dioxide desorbs at a higher temperature from stronger basic sites, the base strength is in the order: BaO/AI203 > SrO/Al203 > CaO/AI203 > MgO/AI~O3, as shown in Fig. 1. These results correspond with those of the unsupported alkaline earth oxides [4]. The amount of basic sites decreases in the order: MgO/AI203 > CaO/AI203 > SrO/AI203 > BaO/A1203. This is in the same order of molar concentrations of alkaline earth oxides in the catalysts. It should be noted that the weight fractions of alkaline earth oxides are the same in this study.

MO g CO a

8
I

A
I ~

SrO

g~

i 200

t 4OO

I 600

I 8O0
I

T(%)

]---------~
I -

Js o t h e r m a [

Fig. 1. TPD spectra of alkaline earth oxide/alumina catalysts

In the case of MgO and CaO, carbon dioxide is reported to adsorb on basic sites as a unidentate complex when a large amount of carbon dioxide is adsorbed, but on both acidic and basic sites as a bidentate complex as the amount of adsorbed carbon dioxide is decreased [5]. The TPD plot of adsorbed CO2 for y-A12Os also exhibits a significant peak at around 100~ This indicates that y-AI203 possesses basic sites even though

86

YU-WEN-CHEN et al.: BASIC1TIES

they are relatively weak. For alkaline earth oxide/alumina catalysts, the amounts of desorbed COz were larger than for A1203. Furthermore, the desorption occurred at higher temperatures for alkaline earth oxide/alumina catalysts than for alumina. There is no desorption peak at around 100~ on alkaline earth oxide/alumina catalysts, indicating that the base sites of alumina are covered by alkaline earth oxides. The basic properties of supported catalysts are the same as those of nonsupported catalysts, indicating that alumina is only a structure promoter in this study.

1.0

.-. 0.8"

0.6

8
"~ 0.4'
r~

0.2

0.0

'

'

'

I00

400

500

600

700

r00

Temp.('C)
Fig. 2. Effect of calcination temperature on the basic sites concentration of CaO/

A1203 The basic properties of alkaline earth oxides are also influenced by the calcination temperature. The strength of basic sites is not influenced by the calcination temperature. However, the amount of basic sites is strongly influenced by the calcination temperature. Typical results are shown in Fig. 2. A calcination temperature of 550~ yields the highest amount of basic sites of CaO.

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