Investigations and Countermeasures for Deactivation of Hydrogen Recombination Catalyst at Hamaoka Units 4 and 5

Abstract

The hydrogen concentration in the outlets of off-gas recombiners increased at Hamaoka Units 4 and 5, and their reactors could not continue the startup operations. Therefore, we investigated why the recombination reactions were deactivated and we selected appropriate countermeasures for both plants. Two types of deactivation mechanisms were found from our investigations. The first cause was the decrease in the active surface area of alumina as support material due to dehydrative condensation. The other cause was the catalyst being poisoned by organic silicon compounds. Organic silicon was introduced from the organosilicon sealant used at the junctions of low-pressure turbines. We also found that a boehmite rich catalyst was deactivated more easily by organic silicon than gamma alumina because boehmite had numerous hydroxyl groups. Finally, we estimated that the deactivation of hydrogen recombination catalysts was caused by two combined factors; these were the characteristics of boehmite as the ingredient of catalysts support and the organic silicon poisoning the catalyst surface. As countermeasures, the boehmite was changed into more stable gamma alumina by adding heat treatment in a hydrogen atmosphere at 500°C for 1 h, and the source of organic silicon, organosilicon sealant, was removed. The improved catalysts were applied at Hamaoka Units 4 and 5. Moreover, the linseed oil that used to be used at the plants was applied again as sealant in the low-pressure turbine casing instead of organosilicon sealant. As a result of the application of these countermeasures, the reactors could be started without increasing the hydrogen concentration at these plants.