Effect of Long-Term High Temperature Oxidation on the Coking Behavior of Ni-Cr Superalloys

The service time of an industrial cracker is strongly dependent on the long-term coking behavior and microstructure stability of the reactor coil alloy. Super alloys are known to withstand temperatures up to even 1400 K. In this work, several commercially available alloys have been first exposed to a long term oxidation at 1423 K for 500 h, so-called metallurgic aging. Subsequently, their coking behavior was evaluated in situ in a thermogravimetric setup under ethane steam cracking conditions (T_gasphase = 1173 K, P_tot = 0.1 MPa, X_C2H6 = 70%, continuous addition of 41 ppmw S/HC of DMDS, dilution δ = 0.33 kg_H2O/kg_HC) and compared with their unaged coking behavior. The tested samples were also examined using scanning electron microscopy and energy diffractive X-ray for surface and cross-section analysis. The alloys characterized by increased Cr-Ni content or the addition of Al showed improved stability against bulk oxidation and anti-coking behavior after application of metallurgic aging due to the formation of more stable oxides on the top surface.