High temperature corrosion of cracking tubes

Abstract

Coils for pyrolysis cracking of hydrocarbons are made of centrifugically cast FeNiCr-alloys and exposed to very severe conditions, high temperatures > 1050°C, oxidizing flue gases at the outside and carburizing atmosphere at the inside. Two tube sections have been investigated after some years operation. In the first case the tube wall was thoroughly carburized, the big size of the internal carbides indicated service at too high temperatures > 1100°C. At such temperatures the protective chromia scale fails by conversion to carbides, allowing ingress of carbon. At the outer wall surface obviously Cr was lost by evaporation as CrO2(OH)2 and CrO3 which is significant at high pO2 and high temperature. In the second case the tube had been operated at more moderate temperature, but showed creep cavities indicating loss of creep strength. This is due to repeated oxidation and loss of the scale by thermal cycling, this process has caused formation of a carbide denuded zone of considerable width at the outer side somewhat less wide at the inner wall. Besides oxide spallation, at the outer wall also evaporation will have played a role.