:Preparation and Activity of Bimodal Alumina based Catalyst for Desulfurization and Demetallation
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A special method was developed for preparing bimodal alumina supports. The catalysts, prepared by adding active metal components to these alumina supports, exhibited high activity for hydrotreating of heavy oils, especially, for hydrodesulfurization and hydrodemetallation.A selected carbon black of high structure (reticulated structure) and large particle size was incorporated into a boehmite gel, kneaded and extruded, and the carbon black was burned out in the presence of an oxygen containing gas to obtain an alumina support which exhibited bimodal pore distribution consisting of two main pore peaks, micropore (under 100Å radius) and mesopore (100-500Å radius) (Fig. 1). Apparently, the mesopore had resulted from the carbon black, because its removal left voids within the alumina solid (Figs. 2, 3).It was also found that both the volume and the size of mesopore could be controlled by changing the amount and the physical properties (particle size and structure) of the carbon black incorporated (Tables 1-3).Even when the active metal components were added to these alumina supports, their bimodal character had not changed (Table 4). The total pore volume and the mesopore volume and its size increased by increasing the amount of carbon black. But the micropore volume was maximized by addition of around 10-20wt% of carbon black (Figs. 4, 5). Using larger carbon black particles, the volume of mesopore decreased, but its size was shifted toward a larger radius that reflected the carbon black particle size (Figs. 7, 8).The desulfurization activity of these catalysts was sufficiently high over a wide range(10-50wt% of carbon black addition). On the other hand, demetallation activity increased abruptly when mesopore appeared distinctly in the pore distribution curve at more than 20-30wt% addition of carbon black (Fig. 6). These facts clearly show the importance of mesopore for demetallation.By varying the calcination temperature of the bimodal alumina, alumina of different pore distribution could be obtained. Higher calcination temperatures decreased the micropore volume and shifted it toward a larger pore size, but the mesopore volume was not affected (Table 5, Figs. 10, 11). Reflecting these changes in pore distribution, the desulfurization activity dropped when the calcination temperature reached about 800°C or higher, but the demetallation activity remained unchanged in the range from 600°C to 1, 000°C (Fig. 12).
- 公益社団法人 石油学会の論文
公益社団法人 石油学会 | 論文
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