The deactivating effect of carbon dioxide on iron-oxide catalyst in the dehydrogenation of methylbutenes

Characteristics of the most energy-intensive second stage of the two-stage production of isoprene from isopentane, i.e., dehydrogenation of methylbutenes are studied to improve the technical and economic performance of the process. The effect of the carbon dioxide formed during self-regeneration of the ironoxide catalyst (according to the reaction Ccoke + 2H2O → 2H2 + CO2) on the conversion of methylbutenes and selectivity with respect to isoprene is investigated. It is found that the presence of CO2 in the reaction batch has a considerable effect on the conversion of methylbutenes; when the content of CO2 in the raw material feed is 1.5 wt %, conversion of methylbutenes is reduced by 5–6%. It is demonstrated that CO2 reversibly deactivates the catalyst and the catalyst activity is restored when its influx is discontined (the yield of isoprene returns gradually to its original value). The recovery rate depends on the concentration and duration of exposure to carbon dioxide. Treatment of the catalyst by steam in the absence of the reaction mixture leads to rapid regeneration of the catalyst. It is concluded that measures to continuously monitor CO2 in the contact gas during the first stage of dehydrogenation, and to select the optimum modes (temperature, steam/raw materials ratio, etc.) for reducing carbon residue during the operation of iron-oxide catalyst in order to implement the two-stage technology for the dehydrogenation of methylbutenes (the main goal of which is to raise the conversion of methylbutenes to 35–40%) are of special importance.